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ENANTIOSELECTIVE C-H AMINATION WITH IRON PHTHALOCYANINE AND DIAMMONIUM TEMPLATE CATALYSTS

20250352988 ยท 2025-11-20

    Inventors

    Cpc classification

    International classification

    Abstract

    Described herein are catalytic systems that can catalyze enantioselective CH functionalization reactions and methods of using thereof are described. These catalytic systems contain iron complexes as host catalysts and diammonium guest templates as co-catalysts. The iron-based host catalysts contain crown-ether phthalocyanine ligands. The diammonium guest templates are bidentate compounds with chirality. The iron-based host catalysts and the bidentate ammonium guest templates can provide a complex steric environment with the for stereospecific and site-selective CH functionalization, such as CH amination. For example, enantioselective CH amination reaction performed using the disclosed methods can achieve high enantiomeric ratio (i.e., at least 2:1) and optionally high yield (i.e., at least 30%).

    Claims

    1. A host catalyst having a structure of: ##STR00117## wherein: (i) each occurrence of A, together with the carbon atoms to which it is attached, forms a crown ether; (ii) each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aralkyl, a halide, a hydroxyl, an alkoxyl, an amino, an amido, a carbonyl, a nitro, a nitrile, or a thiol; and (iii) the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof.

    2. The host catalyst of claim 1, wherein each occurrence of A, together with the carbon atoms to which it is attached, forms a 12-crown-4 ether, a 15-crown-5-ether, an 18-crown-6 ether, a dibenzo-18-crown-6 ether, a 24-crown-8 ether, or an aza-crown ether.

    3. The host catalyst of claim 1, wherein the host catalyst has a structure of: ##STR00118##

    4. The host catalyst of claim 1, wherein each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a hydroxyl, an alkoxyl, or a carbonyl, optionally wherein each occurrence of R.sub.1 and R.sub.2 are hydrogen.

    5. A guest template having a structure of: ##STR00119## wherein: (i) B.sub.1 and B.sub.2 are independently absent, a carbon atom, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, optionally B.sub.1 and B.sub.2 are independently a carbon atom, a substituted or unsubstituted aryl, or a substituted or unsubstituted polyaryl; (ii) R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, optionally R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted aralkyl; (iii) ------ is absent or a bond (single, double, or triple); (iv) X.sub.1 and X.sub.2 are independently absent, oxygen atom, or NR.sub.5, and R.sub.5 is absent, hydrogen, or a substituted or unsubstituted alkyl; (v) L.sub.1 and L.sub.2 are independently absent or ##STR00120## X.sub.3 is a nitrogen atom or CR.sub.6, R.sub.6 is hydrogen or a substituted or unsubstituted alkyl, Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, or a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl; (vi) n.sub.1 and n.sub.2 are independently an integer from 0 to 20; and (vii) the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, an carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof.

    6. The guest template of claim 5, wherein: ##STR00121## is ##STR00122## X.sub.1 and X.sub.2 are independently an oxygen atom or NR.sub.5, R.sub.5 is absent or hydrogen; n.sub.4 and n.sub.5 are independently an integer from 0 to 5; n.sub.6, n.sub.7, n.sub.8, and n.sub.10 are independently an integer from 0 to 4; n.sub.9 and n.sub.11 are independently an integer from 0 to 2; n.sub.12-n.sub.14 are independently an integer from 1 to 6; and R.sub.7-R.sub.14 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, or (b) L and L.sub.2 are independently ##STR00123## wherein X.sub.3 is a nitrogen atom, and wherein Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl, optionally Q.sub.1 and Q.sub.2 are unsubstituted phenyl, or (c) a combination thereof.

    7. A catalytic system comprising: a host catalyst; and a guest template, wherein the host catalyst has the structure of: wherein: ##STR00124## (i) each occurrence of A, together with the carbon atoms to which it is attached, forms a crown ether; (ii) each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aralkyl, a halide, a hydroxyl, an alkoxyl, an amino, an amido, a carbonyl, a nitro, a nitrile, or a thiol; and wherein the guest template has the structure of: ##STR00125## wherein: (i) B.sub.1 and B.sub.2 are independently absent, a carbon atom, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; (ii) R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; (iii) ------ is absent or a bond (single, double, or triple); (iv) X.sub.1 and X.sub.2 are independently absent, oxygen atom, or NR.sub.5, and R.sub.5 is absent, hydrogen, or a substituted or unsubstituted alkyl; (v) L.sub.1 and L.sub.2 are independently absent or ##STR00126## X.sub.3 is a nitrogen atom or CR.sub.6, R.sub.6 is hydrogen or a substituted or unsubstituted alkyl, Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, or a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl; (vi) n.sub.1 and n.sub.2 are independently an integer from 0 to 20; and wherein the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, an carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof.

    8. The catalytic system of claim 7, wherein: (a) the host catalyst and the guest template have a molar ratio ranging from 1:10 to 1:1, from 1:5 to 1:1, such as 1:2; or (b) the host catalyst and the guest template are non-covalently bound to each other, optionally via the crown ether of the host catalyst and the ammonium group of the guest template, and optionally wherein the binding between the host catalyst and the guest template has a log (K) of at least 4.0, such as in a range from 4.0 to about 8.0 or from 4.0 to about 6.0; or (c) a combination thereof.

    9. The catalytic system of claim 7, wherein the host catalyst and the guest template form a structure of: ##STR00127##

    10. The catalytic system of claim 7, wherein: (a) each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a hydroxyl, an alkoxyl, or a carbonyl, optionally each occurrence of R.sub.1 and R.sub.2 are hydrogen; or (b) B.sub.1 and B.sub.2 are independently a carbon atom, a substituted or unsubstituted aryl, or a substituted or unsubstituted polyaryl; and R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted aralkyl; or (c) a combination thereof.

    11. The catalytic system of claim 7, wherein: ##STR00128## X.sub.1 and X.sub.2 are independently an oxygen atom or NR.sub.5, R.sub.5 is absent or hydrogen; n.sub.4 and n.sub.5 are independently an integer from 0 to 5; n.sub.6, n.sub.7, n.sub.8, and n.sub.10 are independently an integer from 0 to 4; n.sub.9 and n.sub.11 are independently an integer from 0 to 2; n.sub.12-n.sub.14 are independently an integer from 1 to 6; and R.sub.7-R.sub.14 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, or (b) L.sub.1 and L.sub.2 are independently ##STR00129## wherein X.sub.3 is a nitrogen atom, and wherein Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl, optionally Q.sub.1 and Q.sub.2 are unsubstituted phenyl, or (c) a combination thereof.

    12. The catalytic system of claim 7, wherein the host catalyst and the guest template form a complex having a structure of: ##STR00130##

    13. A method for asymmetric CH amination of a substrate comprising: (i) maintaining a reaction mixture at room temperature for a period of time sufficient to form a product, wherein the reaction mixture comprises the substrate, a nitrogen-source reactant, the catalytic system of claim 7, and a solvent.

    14. The method of claim 13, wherein the nitrogen-source reactant is RNH.sub.2 or RIN-R, wherein R is SO.sub.2-R.sub.1 or SO.sub.3-R.sub.2; R.sub.1 and R.sub.2 are independently a substituted or unsubstituted phenyl or a substituted or an unsubstituted alkyl (e.g., an unsubstituted linear or branched C1-C10 alkyl, an unsubstituted linear or branched C1-C8 alkyl, an unsubstituted linear or branched C1-C6 alkyl, an unsubstituted linear or branched C1-C4 alkyl, etc., such as a tert-butyl, or a haloalkyl, such as CH.sub.2CCl.sub.3, CCl.sub.3, CH.sub.2CH.sub.2CCl.sub.3, CH.sub.2CCl.sub.2CCl.sub.3, etc.); R is a substituted or unsubstituted phenyl; and the substituents, when present, are independently an unsubstituted alkyl (e.g., any one of those described above, such as a methyl), a halide (e.g., fluoride, chloride, bromide, iodide, etc.), a nitro, a cyano, a nitrile, or a carbonyl.

    15. The method of claim 13, wherein: the substrate has a structure of R-H, and the product has a structure of R-NHR, R is a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted tetralin, a substituted or unsubstituted indane, a substituted or unsubstituted aralkyl, etc.), a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted chromane, a substituted or unsubstituted isochromane, a substituted or unsubstituted thiochromane, a substituted or unsubstituted isothiochromane, dihydrobenzofuran, dihydroisobenzofuran, dihydrobenzothiophene, dihydroisobenzothiophene, etc.), a substituted or unsubstituted cycloalkyl (monocyclic or polycyclic, such as a fused cycloalkyl ring), a substituted or unsubstituted cycloalkenyl (monocyclic or polycyclic, such as a fused cycloalkenyl ring), or a substituted or unsubstituted cycloalkynyl (monocyclic or polycyclic, such as a fused cycloalkynyl ring); and the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a siloxy, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof.

    16. The method of claim 13, wherein: the substrate has a structure of: ##STR00131## and the product has a structure of: ##STR00132## R.sub.15-R.sub.20 are independently hydrogen, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a halide, a hydroxyl, a carbonyl, an amino, an amido, a silyl, or a siloxyl, or R.sub.20 and R.sub.15 together or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, can form a substituted or unsubstituted cycloalkyl (including monocyclic, such as a substituted or unsubstituted cyclopentyl and cyclohexyl, and polycyclic, such as a substituted or unsubstituted fused cycloalkyl ring), a substituted or unsubstituted cycloalkenyl (monocyclic or polycyclic, such as a fused cycloalkenyl ring), a substituted or unsubstituted cycloalkynyl (monocyclic or polycyclic, such as a fused cycloalkynyl ring), a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted oxanyl, a substituted or unsubstituted thianyl, a substituted or unsubstituted oxolanyl, a substituted or unsubstituted thiolanyl, etc.), a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted heteropolyaryl; the substituents, when present, are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a siloxy, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof, such as a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a carbonyl, an oxo, an amino, or an alkoxyl.

    17. The method of claim 16, wherein: (a) R.sub.19 is hydrogen and R.sub.20 is a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, form a substituted or unsubstituted cycloalkyl (including monocyclic, such as a substituted or unsubstituted cyclopentyl and cyclohexyl, and polycyclic, such as a substituted or unsubstituted fused cycloalkyl ring) or a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted oxanyl, a substituted or unsubstituted thianyl, a substituted or unsubstituted oxolanyl, a substituted or unsubstituted thiolanyl, etc.); or (b) R.sub.15-R.sub.18 are independently hydrogen, a halide, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a carbonyl, or a siloxyl; or (c) a combination thereof.

    18. The method of claim 16, wherein R.sub.15, R.sub.16, and R.sub.18 are hydrogen and R.sub.17 is hydrogen, a halide, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a carbonyl, or a siloxyl.

    19. The method of claim 14, wherein R is Tces, Ts, Ns, halobenzene sulfonyl, or halobenzene sulfonate (e.g., a p-chlorobenzene sulfonyl or p-chlorobenzene sulfonate); and R is an unsubstituted phenyl or a phenyl substituted with alkyl or halide (e.g., a chlorobenzene or alkylbenzene).

    20. The method of claim 13, wherein the nitrogen-source reactant in the reaction mixture is PhINTces.

    21. The method of claim 13, wherein the substrate has a structure of: ##STR00133## and the product has a structure of: ##STR00134## ##STR00135## ##STR00136##

    22. The method of claim 13, wherein the substrate and the nitrogen-source reactant have a molar ratio in a range from 10:1 to 1:1 or from 10:1 to 5:1, such as 8:1.

    23. The method of claim 13, wherein the host catalyst has a loading in a range from about 5 mol % to about 30 mol % or from about 10 mol % to about 20 mol %, such as about mol %.

    24. The method of claim 13, wherein: (a) the solvent is CH.sub.3CN, THF, HFIP, or C6H.sub.6, preferably wherein the solvent is CH.sub.3CN; or (b) the reaction mixture further comprises a drying agent or a molecular sieve, such as a 3 molecular sieve, a 4 molecular sieve, or a 5 molecular sieve; or (c) the reaction is performed under an inert gas environment, optionally wherein the inert gas is argon; or (d) a combination thereof.

    25. The method of claim 13, wherein the reaction mixture is maintained in a range from about 30 minutes to about 24 hours, from about 1 hour to about 20 hours, or from about 2 hours to about 18 hours, such as about 16 hours.

    26. The method of claim 13, wherein the product has a yield of at least 30%, at least 40%, at least 50%, in a range from about 30% to about 70%, from about 40% to about 70%, or from about 50% to about 70%.

    27. The method of claim 13, wherein the product has an enantiomeric ratio of at least 2:1, such as in a range from 2:1 to 99:1, from 4:1 to 99:1, from 9:1 to 99:1, or from 19:1 to 99:1, as determined by chiral HPLC.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0033] FIG. 1 is a schematic showing the binding of a guest template with host catalyst Fe(.sup.18-Crown-6PC) to form a supramolecular catalytic system.

    [0034] FIG. 2 shows the structures of exemplary guest tempates grouped by base structure, chiral backbone, and alkyl linker.

    [0035] FIG. 3A is a graph showing the .sup.1H NMR spectra of reaction between Fe-1 and 4c, 4d and 4e. FIG. 3B is a graph showing the UV-vis spectra of reaction between Fe-1 and 4c, 4e and 1 in CH.sub.3CN.

    [0036] FIG. 4A is a scheme that shows the control experiments employed with a 1:2:4 ratio of Fe-1:T2h:Ba(OTf).sub.2 and a 1:2 ratio of Fe-2:T2h as the catalytic system. FIG. 4B is a schematic showing the rationale behind the non-enantioselective processes.

    [0037] FIGS. 5A-5E are graphs showing the results of titration studies: change in 1H-NMR signal for titration between H.sub.2(.sup.18-Crown-6PC) and T2h (FIG. 5A); change of chemical shift of crown ether signal versus the amount of template for T1, T2d, T2e, T2h and T2i (FIG. 5B); change in 1H-NMR signal for titration between H.sub.2(.sup.18-Crown-6PC)/(T2h).sub.2 and Ba(OTf).sub.2(FIG. 5C); change of chemical shift of NH signal versus the amount of Ba(OTf).sub.2 for T1, T2d, T2e, T2h and T2i (FIG. 5D); change in UV-vis signal for titration between Fe-1 and T2h (FIG. 5E).

    [0038] FIG. 6 is a schematic showing the binding between a host catalyst and a guest template for calculating the binding constants.

    [0039] FIG. 7A is a graph showing the .sup.1H-.sup.1H NOSEY NMR of supramolecular catalyst H.sub.2(.sup.18-Crown-6PC)/(T2h).sub.2. FIG. 7B is a graph showing the .sup.1H-.sup.1H NOSEY NMR of supramolecular catalyst H.sub.2(.sup.18-Crown-6PC)/(T2h).sub.2/(Ba(OTf).sub.2) 4. FIG. 7C is a graph showing the .sup.1H DOSY NMR of supramolecular catalyst H.sub.2(.sup.18-Crown-6PC)/(T2h).sub.2.

    [0040] FIG. 8A is a graph showing the CD spectra of T2e from concentration 4.7310.sup.4 to 0.5910.sup.4 M. FIG. 8B is a graph showing the CD spectra of T2d from concentration 4.7310.sup.4 to 1.4810.sup.4M. FIG. 8C is a graph showing the change of maximum of T2h with the addition of Fe-1 and Ba(OTf).sub.2 to the diluted solution of T2h.

    DETAILED DESCRIPTION OF THE INVENTION

    I. Definitions

    [0041] It is to be understood that the disclosed compounds, compositions, and methods are not limited to specific synthetic methods, specific analytical techniques, or to particular reagents unless otherwise specified, and, as such, may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular forms and embodiments only and is not intended to be limiting.

    [0042] Substituted, as used herein, refers to all permissible substituents of the compounds or functional groups described herein. In the broadest sense, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, but are not limited to, halogens, hydroxyl groups, or any other organic groupings containing any number of carbon atoms, preferably 1-14 carbon atoms, and optionally include one or more heteroatoms such as oxygen, sulfur, or nitrogen grouping in linear, branched, or cyclic structural formats. Representative substituents include a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a halogen, a hydroxyl, an alkoxy, a phenoxy, an aroxy, a silyl, a thiol, an alkylthio, a substituted alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, a nitro, a substituted or unsubstituted carbonyl, a carboxyl, an amino, an amido, an oxo, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, an amino acid. Such a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a halogen, a hydroxyl, an alkoxy, a phenoxy, an aroxy, a silyl, a thiol, an alkylthio, a substituted alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, a nitro, a substituted or unsubstituted carbonyl, a carboxyl, an amino, an amido, an oxo, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, and an amino acid can be further substituted.

    [0043] Heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms. It is understood that substitution or substituted includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, i.e., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc.

    [0044] Alkyl, as used herein, refers to the radical of saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl, and cycloalkyl (alicyclic). In some forms, a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone (e.g., C1-C30 for straight chains, C3-C30 for branched chains), 20 or fewer, 15 or fewer, or 10 or fewer. Alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. Likewise, a cycloalkyl is a non-aromatic carbon-based ring composed of at least three carbon atoms, such as a nonaromatic monocyclic or nonaromatic polycyclic ring containing 3-30 carbon atoms, 3-20 carbon atoms, or 3-10 carbon atoms in their ring structure, and have 5, 6 or 7 carbons in the ring structure. Cycloalkyls containing a polycyclic ring system can have two or more non-aromatic rings in which two or more carbons are common to two adjoining rings (i.e., fused cycloalkyl rings). Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctanyl, etc.

    [0045] Substituted alkyl refers to alkyl moieties having one or more substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. Such substituents can be any substituents described above, e.g., halogen (such as fluorine, chlorine, bromine, or iodine), hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), aryl, alkoxyl, aralkyl, phosphonium, phosphanyl, phosphonyl, phosphoryl, phosphate, phosphonate, a phosphinate, amino, amido, amidine, imine, cyano, nitro, azido, oxo, sulfhydryl, thiol, alkylthio, silyl, sulfinyl, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, an aromatic or heteroaromatic moiety. NRR, wherein R and R are independently hydrogen, alkyl, or aryl, and wherein the nitrogen atom is optionally quaternized; SR, wherein R is a phosphonyl, a sulfinyl, a silyl a hydrogen, an alkyl, or an aryl; CN; NO.sub.2; COOH; carboxylate; COR, COOR, or CON(R).sub.2, wherein R is hydrogen, alkyl, or aryl; imino, silyl, ether, haloalkyl (such as CF.sub.3, CH.sub.2CF.sub.3, CCl.sub.3); CN; NCOCOCH.sub.2CH.sub.2; NCOCOCHCH; and NCS; and combinations thereof.

    [0046] It will be understood by those skilled in the art that the moieties substituted on the hydrocarbon chain can themselves be substituted, if appropriate. For instance, the substituents of a substituted alkyl may include halogen, hydroxy, nitro, thiols, amino, aralkyl, azido, imino, amido, phosphonium, phosphanyl, phosphoryl (including phosphonate and phosphinate), oxo, sulfonyl (including sulfate, sulfonamido, sulfamoyl and sulfonate), and silyl groups, as well as ethers, alkylthios, carbonyls (including ketones, aldehydes, carboxylates, and esters), haloalkyls, CN and the like. Cycloalkyls can be substituted in the same manner.

    [0047] Unless the number of carbons is otherwise specified, lower alkyl as used herein means an alkyl group, as defined above, but having from one to ten carbons, more preferably from one to six carbon atoms in its backbone structure. Likewise, lower alkenyl and lower alkynyl have similar chain lengths.

    [0048] Heteroalkyl, as used herein, refers to straight or branched chain, or cyclic carbon-containing alkyl radicals, or combinations thereof, containing at least one heteroatom on the carbon backbone. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, wherein the nitrogen, phosphorous and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. For example, the term heterocycloalkyl group is a cycloalkyl group as defined above where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.

    [0049] The term alkenyl as used herein is a hydrocarbon group of from 2 to 24 carbon atoms and structural formula containing at least one carbon-carbon double bond. Alkenyl groups include straight-chain alkenyl groups, branched-chain alkenyl, and cycloalkenyl. A cycloalkenyl is a non-aromatic carbon-based ring composed of at least three carbon atoms and at least one carbon-carbon double bond, such as a nonaromatic monocyclic or nonaromatic polycyclic ring containing 3-30 carbon atoms and at least one carbon-carbon double bond, 3-20 carbon atoms and at least one carbon-carbon double bond, or 3-10 carbon atoms and at least one carbon-carbon double bond in their ring structure, and have 5, 6 or 7 carbons and at least one carbon-carbon double bond in the ring structure. Cycloalkenyls containing a polycyclic ring system can have two or more non-aromatic rings in which two or more carbons are common to two adjoining rings (i.e., fused cycloalkenyl rings) and contain at least one carbon-carbon double bond. Asymmetric structures such as (AB)CC(CD) are intended to include both the E and Z isomers. This may be presumed in structural formulae herein wherein an asymmetric alkene is present, or it may be explicitly indicated by the bond symbol C. The term alkenyl as used throughout the specification, examples, and claims is intended to include both unsubstituted alkenyls and substituted alkenyls, the latter of which refers to alkenyl moieties having one or more substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. The term alkenyl also includes heteroalkenyl.

    [0050] The term substituted alkenyl refers to alkenyl moieties having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphonium, phosphanyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, oxo, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

    [0051] Heteroalkenyl, as used herein, refers to straight or branched chain, or cyclic carbon-containing alkenyl radicals, or combinations thereof, containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, wherein the nitrogen, phosphorous and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. For example, the term heterocycloalkenyl group is a cycloalkenyl group where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.

    [0052] The term alkynyl group as used herein is a hydrocarbon group of 2 to 24 carbon atoms and a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups include straight-chain alkynyl groups, branched-chain alkynyl, and cycloalkynyl. A cycloalkynyl is a non-aromatic carbon-based ring composed of at least three carbon atoms and at least one carbon-carbon triple bond, such as a nonaromatic monocyclic or nonaromatic polycyclic ring containing 3-30 carbon atoms and at least one carbon-carbon triple bond, 3-20 carbon atoms and at least one carbon-carbon triple bond, or 3-10 carbon atoms and at least one carbon-carbon triple bond in their ring structure, and have 5, 6 or 7 carbons and at least one carbon-carbon triple bond in the ring structure. Cycloalkynyls containing a polycyclic ring system can have two or more non-aromatic rings in which two or more carbons are common to two adjoining rings (i.e., fused cycloalkynyl rings) and contain at least one carbon-carbon triple bond. Asymmetric structures such as (AB)CC(CD) are intended to include both the E and Z isomers. This may be presumed in structural formulae herein wherein an asymmetric alkyne is present, or it may be explicitly indicated by the bond symbol C. The term alkynyl as used throughout the specification, examples, and claims is intended to include both unsubstituted alkynyls and substituted alkynyls, the latter of which refers to alkynyl moieties having one or more substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone. The term alkynyl also includes heteroalkynyl.

    [0053] The term substituted alkynyl refers to alkynyl moieties having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the hydrocarbon backbone. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphonium, phosphanyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

    [0054] Heteroalkynyl, as used herein, refers to straight or branched chain, or cyclic carbon-containing alkynyl radicals, or combinations thereof, containing at least one heteroatom. Suitable heteroatoms include, but are not limited to, O, N, Si, P and S, wherein the nitrogen, phosphorous and sulfur atoms are optionally oxidized, and the nitrogen heteroatom is optionally quaternized. For example, the term heterocycloalkynyl group is a cycloalkynyl group where at least one of the carbon atoms of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulphur, or phosphorus.

    [0055] Aryl, as used herein, refers to C4-C26-membered aromatic rings or fused ring systems containing one aromatic ring and optionally one or more non-aromatic rings. Examples of aryl groups are benzene, tetralin, indane, etc.

    [0056] The term substituted aryl refers to an aryl group, wherein one or more hydrogen atoms on one or more aromatic rings are substituted with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (such as a ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfoxide, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl (such as CF.sub.3, CH.sub.2CF.sub.3, CCl.sub.3), CN, aryl, heteroaryl, and combinations thereof.

    [0057] Heterocyclo and heterocyclyl are used interchangeably, and refer to a cyclic radical attached via a ring carbon or nitrogen atom of a monocyclic ring or polycyclic ring system containing 3-30 ring atoms, 3-20 ring atoms, 3-10 ring atoms, or 5-6 ring atoms, where the polycyclic ring system contains one or more non-aromatic rings and optionally one or more aromatic rings, where at least one non-aromatic ring contains carbon and one to four heteroatoms each selected from the group consisting of non-peroxide oxygen, sulfur, and N(Y) wherein Y is absent or is H, O, C.sub.1-C.sub.10 alkyl, phenyl or benzyl, and optionally containing 1-3 double bonds and optionally substituted with one or more substituents. Heterocyclyl are distinguished from heteroaryl by definition. Heterocycles can be a heterocycloalkyl, a heterocycloalkenyl, a heterocycloalkynyl, etc, such as piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, dihydrofuro[2,3-b]tetrahydrofuran, morpholinyl, piperazinyl, piperidinyl, piperidonyl, 4-piperidonyl, piperonyl, pyranyl, 2H-pyrrolyl, 4H-quinolizinyl, quinuclidinyl, tetrahydrofuranyl, 6H-1,2,5-thiadiazinyl. Heterocyclic groups can optionally be substituted with one or more substituents as defined above for alkyl and aryl.

    [0058] The term heteroaryl refers to C3-C26-membered aromatic rings or fused ring systems containing one aromatic ring and optionally one or more non-aromatic rings, in which one or more carbon atoms on the aromatic ring structure have been substituted with a heteroatom. Suitable heteroatoms include, but are not limited to, oxygen, sulfur, and nitrogen. Examples of heteroaryl groups pyrrole, furan, thiophene, imidazole, oxazole, thiazole, triazole, tetrazole, pyrazole, pyridine, pyrazine, pyridazine and pyrimidine, and the like. Examples of heteroaryl rings include, but are not limited to, benzimidazolyl, benzofuranyl, benzothiofuranyl, benzothiophenyl, benzoxazolyl, benzoxazolinyl, benzthiazolyl, benztriazolyl, benztetrazolyl, benzisoxazolyl, benzisothiazolyl, benzimidazolinyl, carbazolyl, 4aH-carbazolyl, carbolinyl, chromanyl, chromenyl, cinnolinyl, decahydroquinolinyl, 2H,6H-1,5,2-dithiazinyl, furanyl, furazanyl, imidazolidinyl, imidazolinyl, imidazolyl, 1H-indazolyl, indolenyl, indolinyl, indolizinyl, indolyl, 3H-indolyl, isatinoyl, isobenzofuranyl, isochromanyl, isoindazolyl, isoindolinyl, isoindolyl, isoquinolinyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, octahydroisoquinolinyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,3,4-oxadiazolyl, oxazolidinyl, oxazolyl, oxindolyl, pyrimidinyl, phenanthridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxathinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolidinyl, pyrazolinyl, pyrazolyl, pyridazinyl, pyridooxazole, pyridoimidazole, pyridothiazole, pyridinyl, pyridyl, pyrimidinyl, pyrrolidinyl, pyrrolinyl, pyrrolyl, quinazolinyl, quinolinyl, quinoxalinyl, tetrahydroisoquinolinyl, tetrahydroquinolinyl, tetrazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, thianthrenyl, thiazolyl, thienyl, thienothiazolyl, thienooxazolyl, thienoimidazolyl, thiophenyl and xanthenyl. One or more of the rings can be substituted as defined below for substituted heteroaryl.

    [0059] The term substituted heteroaryl refers to a heteroaryl group in which one or more hydrogen atoms on one or more heteroaromatic rings are substituted with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxy, carbonyl (such as a ketone, aldehyde, carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, imino, alkylthio, sulfate, sulfonate, sulfamoyl, sulfoxide, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl (such as CF.sub.3, CH.sub.2CF.sub.3, CCl.sub.3), CN, aryl, heteroaryl, and combinations thereof.

    [0060] The term polyaryl refers to a fused ring system that includes two or more aromatic rings and optionally one or more non-aromatic rings. Examples of polyaryl groups are naphthalene, anthracene, phenanthrene, chrysene, pyrene, corannulene, coronene, etc. When a fused ring system containing two or more aromatic rings and optionally one or more non-aromatic rings, in which one or more carbon atoms on one or more aromatic ring structures have been substituted with a heteroatom, the fused ring system can be referred to as a polyheteroaryl. When a fused ring system containing two or more aromatic rings and optionally one or more non-aromatic rings, in which one or more carbon atoms in the fused ring system is substituted with a heteroatom it can be referred to as a heteropolyaryl. The term substituted polyaryl refers to a polyaryl in which one or more of the aryls are substituted, with one or more substituents including, but not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (or quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfoxide, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, and combinations thereof. When a polyheteroaryl is involved, the chemical moiety can be referred to as a substituted polyheteroaryl.

    [0061] The term cyclic ring or cyclic group refers to a substituted or unsubstituted monocyclic ring or a substituted or unsubstituted polycyclic ring (such as those formed from single or fused ring systems), such as a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted cycloalkynyl, or a substituted or unsubstituted heterocyclyl, that have from three to 30 carbon atoms, as geometric constraints permit. The substituted cycloalkyls, cycloalkenyls, cycloalkynyls, and heterocyclyls are substituted as defined above for the alkyls, alkenyls, alkynyls, and heterocyclyls, respectively.

    [0062] The term aralkyl as used herein is an aryl group or a heteroaryl group having an alkyl, alkynyl, or alkenyl group as defined above attached to the aromatic group, such as an aryl, a heteroaryl, a polyaryl, or a polyheteroaryl. An example of an aralkyl group is a benzyl group.

    [0063] The terms alkoxyl or alkoxy, aroxy or aryloxy, generally describe compounds represented by the formula OR.sup.v, wherein R.sup.v includes, but is not limited to, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocycloalkenyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted arylalkyl, a substituted or unsubstituted heteroalkyl, a substituted or unsubstituted alkylaryl, a substituted or unsubstituted alkylheteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted carbonyl, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, an amido, and an amino. Exemplary alkoxyl groups include methoxy, ethoxy, propyloxy, tert-butoxy and the like. A lower alkoxy group is an alkoxy group containing from one to six carbon atoms. An ether is two functional groups covalently linked by an oxygen as defined below. Accordingly, the substituent of an alkyl that renders that alkyl an ether is or resembles an alkoxyl, such as can be represented by one of O-alkyl, O-alkenyl, O-alkynyl, O-arakyl, -O-aryl, O-heteroaryl, O-polyaryl, O-polyheteroaryl, O-heterocyclyl, etc.

    [0064] The term substituted alkoxy refers to an alkoxy group having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the alkoxy backbone. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphonium, phosphanyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, oxo, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, and combinations thereof.

    [0065] The term ether as used herein is represented by the formula A.sup.2OA.sup.1, where A.sup.2 and A.sup.1 can be, independently, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, a substituted or unsubstituted carbonyl, an alkoxy, an amido, or an amino, described above.

    [0066] The term polyether as used herein is represented by the formula:

    ##STR00015##

    where A.sup.3 can be, independently, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a phosphonium, a phosphanyl, a substituted or unsubstituted carbonyl, an alkoxy, an amido, or an amino, described above; g can be a positive integer from 1 to 30.

    [0067] The term phenoxy is art recognized and refers to a compound of the formula OR.sup.v wherein R.sup.v is C.sub.6H.sub.5 (i.e., OC.sub.6H.sub.5). One of skill in the art recognizes that a phenoxy is a species of the aroxy genus.

    [0068] The term substituted phenoxy refers to a phenoxy group, as defined above, having one or more substituents replacing one or more hydrogen atoms on one or more carbons of the phenyl ring. Such substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphonium, phosphanyl, phosphanyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, and combinations thereof.

    [0069] The terms aroxy and aryloxy, as used interchangeably herein, are represented byO-aryl or O-heteroaryl, wherein aryl and heteroaryl are as defined herein.

    [0070] The terms substituted aroxy and substituted aryloxy, as used interchangeably herein, represent-O-aryl or O-heteroaryl, having one or more substituents replacing one or more hydrogen atoms on one or more ring atoms of the aryl and heteroaryl, as defined herein. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphonium, phosphanyl, phosphanyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

    [0071] The term amino as used herein includes the group

    ##STR00016## [0072] wherein, E is absent, or E is substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, substituted or unsubstituted heterocyclyl, wherein independently of E, R.sup.x, R.sup.xi, and R.sup.xii each independently represent a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, an amido, an amino, or -(CH.sub.2).sub.m-R; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. The term quaternary amino also includes the groups where the nitrogen, R.sup.x, R.sup.xi, and R.sup.xii with the N.sup.+to which they are attached complete a heterocyclyl or heteroaryl having from 3 to 14 atoms in the ring structure. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0073] The terms amide or amido are used interchangeably, refer to both unsubstituted amido and substituted amido and are represented by the general formula:

    ##STR00017## [0074] wherein, E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, or a substituted or unsubstituted heterocyclyl, wherein independently of E, R and R each independently represent a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, an amido, an amino, or -(CH.sub.2).sub.m-R, or R and R taken together with the N atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. In some forms, when E is oxygen, a carbamate is formed. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0075] Carbonyl, as used herein, is art-recognized and includes such moieties as can be represented by the general formula:

    ##STR00018##

    wherein X is a bond, or represents an oxygen or a sulfur, and R represents a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, an amido, an amino, or -(CH.sub.2).sub.m-R, or a pharmaceutical acceptable salt; E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl; R represents a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, an amido, an amino, or -(CH.sub.2).sub.m-R; R represents a hydroxyl group, a substituted orunsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphonium, phosphanyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl). Where X is oxygen and R is defined as above, the moiety is also referred to as a carboxyl group. When X is oxygen and R is hydrogen, the formula represents a carboxylic acid. Where X is oxygen and Ris hydrogen, the formula represents a formate. Where X is oxygen and R or Ris not hydrogen, the formula represents an ester. In general, where the oxygen atom of the above formula is replaced by a sulfur atom, the formula represents a thiocarbonyl group. Where X is sulfur and R or Ris not hydrogen, the formula represents a thioester. Where X is sulfur and R is hydrogen, the formula represents a thiocarboxylic acid. Where X is sulfur and Ris hydrogen, the formula represents a thioformate. Where X is a bond and R is not hydrogen, the above formula represents a ketone. Where X is a bond and R is hydrogen, the above formula represents an aldehyde.

    [0076] The term phosphanyl is represented by the formula

    ##STR00019## [0077] wherein, E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, wherein independently of E, R.sup.vi and R.sup.vii each independently represent a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g., a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, an amido, an amino, or -(CH.sub.2).sub.m-R, or R.sup.vi and R.sup.vii taken together with the P atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0078] The term phosphonium is represented by the formula

    ##STR00020## [0079] wherein, E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, wherein independently of E, R.sup.vi, R.sup.vii, and R.sup.viii each independently represent a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, an amido, an amino, or -(CH.sub.2).sub.m-R, or R.sup.vi, R.sup.vii, and R.sup.viii taken together with the P.sup.+atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0080] The term phosphonyl is represented by the formula

    ##STR00021## [0081] wherein E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl (e.g., a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, oxygen, alkoxy, aroxy, or substituted alkoxy or substituted aroxy, wherein, independently of E, R.sup.vi and R.sup.vii are independently a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a silyl, a thiol, an amido, an amino, or -(CH.sub.2).sub.m-R, or R.sup.vi and R.sup.vii taken together with the P atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0082] The term phosphoryl defines a phosphonyl in which E is absent, oxygen, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above, and independently of E, R.sup.vi and R.sup.vii are independently hydroxyl, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above. When E is oxygen, the phosphoryl cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. When E, R.sup.vi and R.sup.vii are substituted, the substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0083] The term sulfinyl is represented by the formula

    ##STR00022## [0084] wherein E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl (e.g., a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, wherein independently of E, R represents a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, a phosphonyl, a silyl, a thiol, an amido, an amino, or -(CH.sub.2).sub.m-R, or E and R taken together with the S atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0085] The term sulfonyl is represented by the formula

    ##STR00023## [0086] wherein E is absent, or E is a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl (e.g., a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, wherein independently of E, R represents a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, an amido, an amino, or -(CH.sub.2).sub.m-R, or E and R taken together with the S atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0087] The term sulfonic acid refers to a sulfonyl, as defined above, wherein R is hydroxyl, and E is absent, or E is substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, or substituted or unsubstituted heteroaryl. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0088] The term sulfate refers to a sulfonyl, as defined above, wherein E is absent, oxygen, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above, and R is independently hydroxyl, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above. When E is oxygen, the sulfate cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0089] The term sulfonate refers to a sulfonyl, as defined above, wherein E is oxygen, alkoxy, aroxy, substituted alkoxy or substituted aroxy, as defined above, and R is independently hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted amino, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aralkyl, substituted or unsubstituted alkylaryl, substituted or unsubstituted arylalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, -(CH.sub.2).sub.m-R, R represents a hydroxy group, substituted or unsubstituted carbonyl group, an aryl, a cycloalkyl ring, a cycloalkenyl ring, a heterocycle, an amido, an amino, or a polycycle; and m is zero or an integer ranging from 1 to 8. When E is oxygen, sulfonate cannot be attached to another chemical species, such as to form an oxygen-oxygen bond, or other unstable bonds, as understood by one of ordinary skill in the art. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0090] The term sulfamoyl refers to a sulfonamide or sulfonamide represented by the formula

    ##STR00024##

    wherein E is absent, or E is substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aralkyl (e.g., a substituted or unsubstituted alkylaryl, a substituted or unsubstituted cycloalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, wherein independently of E, R and R each independently represent a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted carbonyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted heterocyclyl, a hydroxyl, an alkoxy, a phosphonium, a phosphanyl, an amido, an amino, or -(CH.sub.2).sub.m-R, or R and R taken together with the N atom to which they are attached complete a heterocycle having from 3 to 14 atoms in the ring structure; R represents a hydroxyl group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted aryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, an alkoxy, a phosphonium, a phosphanyl, an amido, or an amino; and m is zero or an integer ranging from 1 to 8. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof. It is understood by those of ordinary skill in the art, that the E groups listed above are divalent (e.g., methylene, ethane-1,2-diyl, ethene-1,2-diyl, 1,4-phenylene, cyclohexane-1,2-diyl).

    [0091] The term silyl group as used herein is represented by the formula SiRRR, where R, R, and R can be, independently, a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted carbonyl, a phosphonium, a phosphanyl, a phosphonyl, a sulfinyl, a thiol, an amido, an amino, an alkoxy, or an oxo, described above. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

    [0092] The terms thiol are used interchangeably and are represented bySR, where R can be a hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted aralkyl (e.g. a substituted or unsubstituted alkylaryl, a substituted or unsubstituted arylalkyl, etc.), a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted carbonyl, a phosphonium, a phosphanyl, an amido, an amino, an alkoxy, an oxo, a phosphonyl, a sulfinyl, or a silyl, described above. Such substituents can be any substituents described above, e.g., halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, carbonyl (such as a carboxyl, alkoxycarbonyl, formyl, or an acyl), silyl, ether, ester, thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), alkoxyl, phosphoryl, phosphate, phosphonate, phosphinate, amino (e.g. quarternized amino), amido, amidine, imine, cyano, nitro, azido, sulfhydryl, alkylthio, sulfate, sulfonate, sulfamoyl, sulfonamido, sulfonyl, heterocyclyl, alkylaryl, haloalkyl, CN, aryl, heteroaryl, polyaryl, polyheteroaryl, and combinations thereof.

    [0093] The disclosed compounds and substituent groups, can, independently, possess two or more of the groups listed above. For example, if the compound or substituent group is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can be substituted with a hydroxyl group, an alkoxy group, etc. Depending upon the groups that are selected, a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase an alkyl group comprising an ester group, the ester group can be incorporated within the backbone of the alkyl group. Alternatively, the ester can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.

    [0094] The compounds and substituents can be substituted, independently, with the substituents described above in the definition of substituted.

    [0095] The numerical ranges disclose individually each possible number that such a range could reasonably encompass, as well as any sub-ranges and combinations of sub-ranges encompassed therein. For example, in a given range carbon range of C.sub.3-C.sub.9, the range also discloses C.sub.3, C.sub.4, C.sub.5, C.sub.6, C.sub.7, C.sub.8, and Co, as well as any subrange between these numbers (for example, C.sub.4-C.sub.6), and any possible combination of ranges possible between these values. In yet another example, a given temperature range may be from about 25 C. to 30 C., where the range also discloses temperatures that can be selected independently from about 25, 26, 27, 28, 29, and 30 C., as well as any range between these numbers (for example, 26 to 28 C.), and any possible combination of ranges between these values.

    [0096] Use of the term about is intended to describe values either above or below the stated value, which the term about modifies, to be within a range of approximately +/10%. When the term about is used before a range of numbers (i.e., about 1-5) or before a series of numbers (i.e., about 1, 2, 3, 4, etc.) it is intended to modify both ends of the range of numbers and/or each of the numbers recited in the entire series, unless specified otherwise.

    [0097] The disclosed compounds and substituent groups, can, independently, possess two or more of the groups listed above. For example, if the compound or substituent group is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can be substituted with a hydroxyl group, an alkoxy group, etc. Depending upon the groups that are selected, a first group can be incorporated within second group or, alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase an alkyl group comprising an ester group, the ester group can be incorporated within the backbone of the alkyl group. Alternatively, the ester can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.

    [0098] The compounds and substituents can be substituted with, independently, with the substituents described above in the definition of substituted.

    II. Compositions

    [0099] Catalytic systems that can catalyze CH functionalization reactions, such as CH amination, with enantioselectivity have been developed. These catalytic systems contain iron complexes as host catalysts and diammonium guest templates as co-catalysts. The iron-based host catalysts contain crown-ether phthalocyanine as supporting ligands. The diammonium guest templates are bidentate compounds with chirality. The structures of the iron-based host catalysts and bidentate ammonium guest templates of the catalytic system allow them to interact with each other and thereby provide a complex steric environment, which allows for stereospecific and site-selective CH functionalization, such as enantioselective CH amination. The terms enantioselective CH amination and asymmetric CH amination are used interchangeably herein. For example, the disclosed catalytic systems can catalyze CH amination with high enantioselectivity (i.e., at least 2:1) and optionally high yield (i.e., >30%), under mild reaction conditions, such as at room temperature.

    [0100] Without being bound to any theories, it is believed that the bidentate ammonium guest template can spontaneously self-assemble with the iron-based host catalysts through non-covalent interactions between the ammonium groups and the crown-ether components of the host catalyst to form a supramolecular structure. The strong binding affinity (i.e., a log (K) of at least 4.0) of the bidentate ammonium guest templates for the crown-ether containing host catalysts stabilizes the overall supramolecular structure and provides thermal stability for the catalytic system. Such a thermal stable supramolecular structure can provide an advantageous steric environment for stereospecific and site-selective CH functionalization, such as enantioselective CH amination.

    A. Iron-Based Host Catalysts

    [0101] The disclosed catalytic system contains an iron-based host catalyst (also referred to herein as the host catalyst). The host catalyst contains crown-ether phthalocyanine as supporting ligands. The x-accepting phthalocyanine scaffold of the ligands can provide elevated reactivity and stability for the iron-based host catalysts. The inclusion of crown-ether substituents onto the core phthalocyanine scaffold can provide supramolecular chemistry for creating structural complexity. For example, the crown-ether components of the supporting ligands allow for non-covalent interactions (such as ionic interactions, hydrogen bonding, Van der Waals forces, effects, hydrophobic/hydrophilic effects, etc.) with a variety of functional groups (such as ammonium, for example, ammonium groups of a bidentate ammonium guest template as described herein) to create a complex steric environment for stereospecific and site-selective reactions (such as enantioselective CH aminations).

    [0102] The disclosed iron-based host catalyst can have the structure of Formula I:

    ##STR00025## [0103] wherein: (i) each occurrence of A, together with the carbon atoms to which it is attached, can form a crown ether; (ii) each occurrence of R.sub.1 and R.sub.2 can be independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aralkyl, a halide, a hydroxyl, an alkoxyl, an amino, an amido, a carbonyl, a nitro, a nitrile, or a thiol; and (iii) the substituents can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof.

    [0104] In some forms of Formula I, each occurrence of A, together with the carbon atoms to which it is attached, can form a 12-crown-4 ether, a 15-crown-5-ether, an 18-crown-6 ether, a dibenzo-18-crown-6 ether, a 24-crown-8 ether, or an aza-crown ether.

    [0105] In some forms, the host catalyst can have the structure of Formula II:

    ##STR00026## [0106] wherein R.sub.1 and R.sub.2 are as defined above for Formula I.

    [0107] For any one of Formula I and Formula II, each occurrence of R.sub.1 and R.sub.2 can be independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a hydroxyl, an alkoxyl, or a carbonyl. For example, in some forms, each occurrence of R.sub.1 and R.sub.2 of Formula I and/or Formula II are hydrogen.

    [0108] In some forms, the host catalyst can have the following structure:

    ##STR00027##

    B. Diammonium Guest Templates

    [0109] The disclosed catalytic system further contains a bidentate ammonium guest template as a co-catalyst (also referred to herein as the guest template or diammonium template). The guest template contains a chiral backbone and at least two terminal ammonium groups that can bind to the crown-ether components of the host catalyst via non-covalent interactions, such as by hydrogen bonding.

    [0110] The disclosed guest templates can have the structure of Formula III:

    ##STR00028## [0111] wherein: (i) B.sub.1 and B.sub.2 can be independently absent, a carbon atom, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; (ii) R.sub.3 and R.sub.4 can be independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; (iii) custom-character can be absent or a bond (single, double, or triple); (iv) X.sub.1 and X.sub.2 can be independently absent, oxygen atom, or NR.sub.5, and R.sub.5 is absent, hydrogen, or a substituted or unsubstituted alkyl; (v) L.sub.1 and L.sub.2 can be independently absent or

    ##STR00029##

    X.sub.3 can be a nitrogen atom or CR.sub.6, R.sub.6 is hydrogen or a substituted or unsubstituted alkyl, Q.sub.1 and Q.sub.2 can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, or a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl; (vi) n.sub.1 and n.sub.2 can be independently an integer from 0 to 20; and (vii) the substituents can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, an carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof.

    [0112] In some forms of Formula III, B.sub.1 and B.sub.2 can be independently a carbon atom, a substituted or unsubstituted aryl, or a substituted or unsubstituted polyaryl; and R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted aralkyl.

    [0113] Typically, the

    ##STR00030##

    of Formula III contains one or more chiral centers. For example, in some forms of Formula III,

    ##STR00031##

    can be one of the following:

    ##STR00032## [0114] wherein X.sub.1 and X.sub.2 can be independently an oxygen atom or NR.sub.5, R.sub.5 can be absent or hydrogen; n.sub.4 and n.sub.5 can be independently an integer from 0 to 5; n.sub.6, n.sub.7, n.sub.8, and n.sub.10 can be independently an integer from 0 to 4; n.sub.9 and n.sub.11 can be independently an integer from 0 to 2; n.sub.12-n.sub.14 can be independently an integer from 1 to 6; and R.sub.7-R.sub.14 can be independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic.

    [0115] In some forms of Formula III, L.sub.1 and L.sub.2 can be independently

    ##STR00033##

    wherein X.sub.3 can be a nitrogen atom, and wherein Q.sub.1 and Q.sub.2 can be independently a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl. For example, Q.sub.1 and Q.sub.2 are unsubstituted phenyl.

    [0116] In some forms, the guest template is in a salt form of the structure of Formula III. In these forms, the guest template contains a cationic component having the structure of Formula III and an anion. Any suitable anions can be used to form the guest template, for example, tetrafluoroborate, acetate, aspartate, benzoate, besylate, bicarbonate/carbonate, bisulphate/sulphate, borate, camsylate, citrate, edisylate, esylate, formate, fumarate, gluceptate, gluconate, glucuronate, hexafluorophosphate, hibenzate, hydrochloride/chloride, hydrobromide/bromide, hydroiodide/iodide, isethionate, lactate, malate, maleate, malonate, mesylate, methylsulphate, naphthylate, 2-napsylate, nicotinate, nitrate, orotate, oxalate, palmitate, pamoate, phosphate/hydrogen phosphate/dihydrogen phosphate, saccharate, stearate, succinate, tartrate, tosylate and trifluoroacetate salts. In some forms, the guest template contains a cationic component having the structure of Formula III and tetrafluoroborate anions.

    [0117] In some forms, the guest template can have the structure of any one of the following:

    ##STR00034## ##STR00035## ##STR00036##

    C. Catalytic Systems

    [0118] The catalytic systems disclosed herein contain an iron-based host catalyst and a bidentate ammonium guest template, such as any one of the host catalysts and any one of the guest templates described above. Generally, the host catalyst and the guest template of the catalytic system can have a molar ratio ranging from 1:10 to 1:1, from 1:5 to 1:1, such as 1:2.

    [0119] The structures of the host catalyst and the guest template allow them to interact with each other, such as by non-covalent interactions, and thereby provide a complex steric environment suitable for stereospecific and site-selective CH functionalization, such as CH aminations. For example, without being bound to any theories, it is believed that the bidentate ammonium guest template can spontaneously self-assemble with the iron-based host catalysts through non-covalent interactions between the ammonium groups and the crown-ether components of the host catalyst to form a supramolecular structure, such as the structure of Formula IV shown below. The supramolecular structures formed by the host catalyst and guest template can be examined using spectroscopic methods, for example, by using NMR, UV-vis, and/or CD spectroscopies.

    ##STR00037##

    [0120] The supramolecular structure can provide a steric environment for stereospecific and site-selective CH functionalization, such as CH aminations. For example, the disclosed catalytic systems can catalyze CH amination with high enantioselectivity (i.e., at least 2:1).

    [0121] Further, the bidentate ammonium guest templates can bind the crown-ether containing host catalysts with a strong binding affinity (i.e., a log (K) of at least 4.0). For example, the binding between the host catalyst and the guest template has a log (K) of at least 4.0, such as in a range from 4.0 to about 8.0 or from 4.0 to about 6.0. Such a binding affinity can stabilize the overall supramolecular structure and thereby provide thermal stability for the catalytic system. This allows for enantioselective chemical reactions, such as enantioselective CH aminations, under room temperature, as compared to the low temperatures (typically from 10 C. to 35 C.) required in enantioselective CH aminations using art-known Rhodium catalysts (see, for example, C. Liang, et al., Angew. Chem. Int. Ed. 2006, 45, 4641-4644; C. Liang, et al., J. Am. Chem. Soc. 2008, 130, 343-350). For example, the disclosed catalytic systems can catalyze CH aminations with high enantioselectivity (i.e., at least 2:1) and optionally high yield (i.e., 30%), under mild reaction conditions, such as at room temperature.

    [0122] In some forms, the host catalyst and guest template can form any one of the following supramolecular structures:

    ##STR00038##

    [0123] In some forms, for any of Formulae I-V described above, the substituents, when present, can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted alkylaryl (e.g. benzyl), a carbonyl (e.g. carboxyl, ester, etc.), an alkoxy (e.g. methoxy, ethoxy, aryloxy, benzoether, etc.), a halide, a hydroxyl, or a haloalkyl, or a combination thereof.

    [0124] For any of Formulae I-V described above, the alkyl can be a linear alkyl, a branched alkyl, or a cyclic alkyl (either monocyclic or polycyclic). The terms cyclic alkyl and cycloalkyl are used interchangeably herein. Exemplary alkyl include a linear C.sub.1-C.sub.30 alkyl, a branched C.sub.4-C.sub.30 alkyl, a cyclic C.sub.3-C.sub.30 alkyl, a linear C.sub.1-C.sub.20 alkyl, a branched C.sub.4-C.sub.20 alkyl, a cyclic C.sub.3-C.sub.20 alkyl, a linear C.sub.1-C.sub.10 alkyl, a branched C.sub.4-C.sub.10 alkyl, a cyclic C.sub.3-C.sub.10 alkyl, a linear C.sub.1-C.sub.6 alkyl, a branched C.sub.4-C.sub.6 alkyl, a cyclic C.sub.3-C.sub.6 alkyl, a linear C.sub.1-C.sub.4 alkyl, cyclic C.sub.3-C.sub.4 alkyl, such as a linear C.sub.1-C.sub.10, C.sub.1-C.sub.9, C.sub.1-C.sub.8, C.sub.1-C.sub.7, C.sub.1-C.sub.6, C.sub.1-C.sub.5, C.sub.1-C.sub.4, C.sub.1-C.sub.3, or C.sub.1-C.sub.2 alkyl group, a branched C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, or C.sub.3-C.sub.4 alkyl group, or a cyclic C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, or C.sub.3-C.sub.4 alkyl group. The cyclic alkyl can be a monocyclic or polycyclic alkyl, such as a C.sub.4-C.sub.30, C.sub.4-C.sub.25, C.sub.4-C.sub.20, C.sub.4-C.sub.18, C.sub.4-C.sub.16, C.sub.4-C.sub.15, C.sub.4-C.sub.14, C.sub.4-C.sub.13, C.sub.4-C.sub.12, C.sub.4-C.sub.10, C.sub.4-C.sub.9, C.sub.4-C.sub.8, C.sub.4-C.sub.7, C.sub.4-C.sub.6, or C.sub.4-C.sub.5 monocyclic or polycyclic alkyl group.

    [0125] For any of Formulae I-V described above, the alkenyl can be a linear alkenyl, a branched alkenyl, or a cyclic alkenyl (either monocyclic or polycyclic). The terms cyclic alkenyl and cycloalkenyl are used interchangeably herein. Exemplary alkenyl include a linear C.sub.2-C.sub.30 alkenyl, a branched C.sub.4-C.sub.30 alkenyl, a cyclic C.sub.3-C.sub.30 alkenyl, a linear C.sub.2-C.sub.20 alkenyl, a branched C.sub.4-C.sub.20 alkenyl, a cyclic C.sub.3-C.sub.20 alkenyl, a linear C.sub.2-C.sub.10 alkenyl, a branched C.sub.4-C.sub.10 alkenyl, a cyclic C.sub.3-C.sub.10 alkenyl, a linear C.sub.2-C.sub.6 alkenyl, a branched C.sub.4-C.sub.6 alkenyl, a cyclic C.sub.3-C.sub.6 alkenyl, a linear C.sub.2-C.sub.4 alkenyl, cyclic C.sub.3-C.sub.4 alkenyl, such as a linear C.sub.2-C.sub.10, C.sub.2-C.sub.9, C.sub.2-C.sub.8, C.sub.2-C.sub.7, C.sub.2-C.sub.6, C.sub.2-C.sub.5, C.sub.2-C.sub.4, C.sub.2-C.sub.3, C.sub.2 alkenyl group, a branched C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkenyl group, or a cyclic C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkenyl group. The cyclic alkenyl can be a monocyclic or polycyclic alkenyl, such as a C.sub.4-C.sub.30, C.sub.4-C.sub.25, C.sub.4-C.sub.20, C.sub.4-C.sub.18, C.sub.4-C.sub.16, C.sub.4-C.sub.15, C.sub.4-C.sub.14, C.sub.4-C.sub.13, C.sub.4-C.sub.12, C.sub.4-C.sub.10, C.sub.4-C.sub.9, C.sub.4-C.sub.8, C.sub.4- C.sub.7, C.sub.4-C.sub.6, or C.sub.4-C.sub.5 monocylcic or polycyclic alkenyl group.

    [0126] For any of Formulae I-V described above, the alkynyl can be a linear alkynyl, a branched alkynyl, or a cyclic alkynyl (either monocyclic or polycyclic). The terms cyclic alkynyl and cycloalkynyl are used interchangeably herein. Exemplary alkynyl include a linear C.sub.2-C.sub.30 alkynyl, a branched C.sub.4-C.sub.30 alkynyl, a cyclic C.sub.3-C.sub.30 alkynyl, a linear C.sub.2-C.sub.20 alkynyl, a branched C.sub.4-C.sub.20 alkynyl, a cyclic C.sub.3-C.sub.20 alkynyl, a linear C.sub.2-C.sub.10 alkynyl, a branched C.sub.4-C.sub.10 alkynyl, a cyclic C.sub.3-C.sub.10 alkynyl, a linear C.sub.2-C.sub.6 alkynyl, a branched C.sub.4-C.sub.6 alkynyl, a cyclic C.sub.3-C.sub.6 alkynyl, a linear C.sub.2-C.sub.4 alkynyl, cyclic C.sub.3-C.sub.4 alkynyl, such as a linear C.sub.2-C.sub.10, C.sub.2-C.sub.9, C.sub.2-C.sub.8, C.sub.2-C.sub.7, C.sub.2-C.sub.6, C.sub.2-C.sub.5, C.sub.2-C.sub.4, C.sub.2-C.sub.3, C.sub.2 alkynyl group, a branched C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkynyl group, or a cyclic C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkynyl group. The cyclic alkynyl can be a monocyclic or polycyclic alkynyl, such as a C.sub.4-C.sub.30, C.sub.4-C.sub.25, C.sub.4-C.sub.20, C.sub.4-C.sub.18, C.sub.4-C.sub.16, C.sub.4-C.sub.15, C.sub.4-C.sub.14, C.sub.4-C.sub.13, C.sub.4-C.sub.12, C.sub.4-C.sub.10, C.sub.4-C.sub.9, C.sub.4-C.sub.8, C.sub.4- C.sub.7, C.sub.4-C.sub.6, or C.sub.4-C.sub.5 monocyclic or polycyclic alkynyl group.

    [0127] It is understood that any of the exemplary alkyl, alkenyl, and alkynyl groups can be heteroalkyl, heteroalkenyl, and heteroalkynyl, respectively.

    [0128] For any of Formulae I-V described above, the aryl group can be a C.sub.5-C.sub.30 aryl, a C.sub.5-C.sub.20 aryl, a C.sub.5-C.sub.12 aryl, a C.sub.5-C.sub.11 aryl, a C.sub.5-C.sub.9 aryl, a C.sub.6-C.sub.20 aryl, a C.sub.6-C.sub.12 aryl, a C.sub.6-C.sub.11 aryl, or a C.sub.6-C.sub.9 aryl. It is understood that the aryl can be a heteroaryl, such as a C.sub.5-C.sub.30 heteroaryl, a C.sub.5-C.sub.20 heteroaryl, a C.sub.5-C.sub.12 heteroaryl, a C.sub.5-C.sub.11 heteroaryl, a C.sub.5-C.sub.9 heteroaryl, a C.sub.6-C.sub.30 heteroaryl, a C.sub.6-C.sub.20 heteroaryl, a C.sub.6-C.sub.12 heteroaryl, a C.sub.6-C.sub.11 heteroaryl, or a C.sub.6-C.sub.9 heteroaryl. For any of Formulae I, Ia, II, III, and IV, the polyaryl group can be a C.sub.10-C.sub.30 polyaryl, a C.sub.10-C.sub.20 polyaryl, a C.sub.10-C.sub.12 polyaryl, a C.sub.10-C.sub.11 polyaryl, or a C.sub.12-C.sub.20 polyaryl. It is understood that the aryl can be a polyheteroaryl, such as a C.sub.10-C.sub.30 polyheteroaryl, a C.sub.10-C.sub.20 polyheteroaryl, a C.sub.10-C.sub.12 polyheteroaryl, a C.sub.10-C.sub.11 polyheteroaryl, or a C.sub.12-C.sub.20 polyheteroaryl.

    III. Methods of Making and Reagents Thereof

    [0129] The iron-based host catalysts, the ligands forming the host catalysts, and the diammonium templates described herein can be synthesized using methods known in the art of organic chemical synthesis.

    [0130] The target host catalysts can be synthesized by reacting a corresponding crown-ether phthalocyanine ligand with an iron precursor in a suitable solvent. The corresponding ligand(s) can be prepared using methods known in the art, such as those described in the Examples. The reaction solution containing the corresponding crown-ether phthalocyanine ligand and the iron precursor can be stirred at room temperature and optionally under an inert gas atmosphere, such as nitrogen atmosphere, for a suitable time to form a product containing the target iron-based host catalysts. The product containing the target iron-based host catalysts can be purified and optionally recrystallized to provide the target iron-based host catalysts.

    [0131] The diammonium templates can be prepared using methods known in the art, such as those described in the Examples.

    [0132] More specific reagents, reaction conditions, and iron-based host catalysts and diammonium templates formed are described in the Examples.

    IV. Methods of Using

    [0133] The catalytic systems described herein are thermal stable and can provide a steric environment for chemical reactions. For example, the supramolecular structure formed by non-covalent interactions between the host catalyst and guest template can provide a steric environment for stereospecific and site-selective CH functionalization, such as C-H aminations. Further, the bidentate ammonium guest templates can bind the crown-ether containing host catalysts with a strong binding affinity (i.e., a log (K) of at least 4.0), and thereby provide thermal stability for the catalytic system. This allows for enantioselective chemical reactions, such as enantioselective CH aminations, under room temperature, as compared to the low temperatures (typically from 10 C. to 35 C.) required in enantioselective CH aminations using art-known Rhodium catalysts (see, for example, C. Liang, et al., Angew. Chem. Int. Ed. 2006, 45, 4641-4644; C. Liang, et al., J. Am. Chem. Soc. 2008, 130, 343-350). Accordingly, the catalytic systems disclosed herein are particularly suitable for use in enantioselective reactions, such as enantioselective C-H functionalization reactions, under mild reaction conditions, such as at room temperature (i.e., 20-22 C. at 1 atm). For example, the disclosed catalytic systems can catalyze CH amination of a variety of substrates to produce aminated products with high enantioselectivity (i.e., at least 2:1) and optionally high yield (i.e., 30%), at room temperature.

    [0134] Generally, the methods of catalyzing an enantioselective CH amination of a substrate using the catalytic system disclosed herein include: (i) maintaining a reaction mixture at room temperature for a period of time sufficient to form an aminated product, wherein the reaction mixture contains the substrate, a nitrogen-source reactant, the catalytic system described herein, and a solvent.

    [0135] Typically, the host catalyst of the catalytic system used in the method for catalyzing enantioselective CH amination reaction can have a loading in a range from about 5 mol % to about 30 mol % or from about 10 mol % to about 20 mol %, such as about 15 mol % in the reaction mixture. The loading of the host catalyst in the reaction mixture can be calculated using the formula: mol % of the host catalyst= [(the no. of moles of the host catalyst)/(the no. of moles of limiting reagent]100%. For example, if 1. equiv. PhINTces is the limiting reagent, then 0.15 equiv. of the Fe catalysts can be used.

    [0136] The nitrogen-source reactant in the reaction mixture of the disclosed method can be any suitable compounds capable of supplying nitrogen atom(s) or a functional group containing nitrogen atom(s) that replaces a hydrogen of the substrate to form the aminated product. In some forms, the nitrogen-source reactant in the reaction mixture can be RNH.sub.2 or RIN-R, wherein R can be SO.sub.2-R.sub.1 or SO.sub.3-R.sub.2; R.sub.1 and R.sub.2 can be independently a substituted or unsubstituted phenyl or a substituted or an unsubstituted alkyl (e.g., an unsubstituted linear or branched C.sub.1-C.sub.10 alkyl, an unsubstituted linear or branched C.sub.1-C.sub.8 alkyl, an unsubstituted linear or branched C.sub.1-C.sub.6 alkyl, an unsubstituted linear or branched C.sub.1-C.sub.4 alkyl, etc., such as a tert-butyl, or a haloalkyl, such as CH.sub.2CCl.sub.3, CCl.sub.3, CH.sub.2CH.sub.2CCl.sub.3, CH.sub.2CCl.sub.2CCl.sub.3, etc.); R can be a substituted or unsubstituted phenyl; and the substituents, when present, can be independently an unsubstituted alkyl (e.g., any one of those described above, such as a methyl), a halide (such as chloride), a nitro, a cyano, a nitrile, or a carbonyl. In some forms, the nitrogen-source reactant in the reaction mixture can be RNH.sub.2 or RIN-R, wherein R can be Tces, Ts, Ns, or o/p/m-halobenzene sulfonyl or sulfonate (such as a p-chlorobenzene sulfonyl or p-chlorobenzene sulfonate); and R can be an unsubstituted phenyl or a phenyl substituted with alkyl or halide (such as a chlorobenzene or alkylbenzene) at any suitable position(s) on the benzene ring. In some forms, the nitrogen-source reactant in the reaction mixture can be PhINTces.

    [0137] In some forms of the method, the substrate used in the reaction mixture for enantioselective CH amination reaction can have a structure of R-H, and the aminated product formed by enantioselective CH amination reaction the can have a structure of R-NHR, wherein R can be a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted tetralin, a substituted or unsubstituted indane, a substituted or unsubstituted aralkyl, etc.), a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted chromane, a substituted or unsubstituted isochromane, a substituted or unsubstituted thiochromane, a substituted or unsubstituted isothiochromane, dihydrobenzofuran, dihydroisobenzofuran, dihydrobenzothiophene, dihydroisobenzothiophene, etc.), a substituted or unsubstituted cycloalkyl (monocyclic or polycyclic, such as a fused cycloalkyl ring), a substituted or unsubstituted cycloalkenyl (monocyclic or polycyclic, such as a fused cycloalkenyl ring), or a substituted or unsubstituted cycloalkynyl (monocyclic or polycyclic, such as a fused cycloalkynyl ring); the substituents can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a siloxy, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof; and R can be any one of those described above for RNH.sub.2 or RIN-R, such as Tces, Ts, Ns, or o/p/m-halobenzene sulfonyl or sulfonate (such as a p-chlorobenzene sulfonyl or p-chlorobenzene sulfonate). In some forms, R can be a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted tetralin, a substituted or unsubstituted indane, a substituted or unsubstituted aralkyl, etc.), a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted chromane, a substituted or unsubstituted isochromane, a substituted or unsubstituted thiochromane, a substituted or unsubstituted isothiochromane, dihydrobenzofuran, dihydroisobenzofuran, dihydrobenzothiophene, dihydroisobenzothiophene, etc.).

    [0138] In some forms of the method, the substrate used in the reaction mixture for enantioselective CH amination reaction can have the structure of Formula VI and the aminated product formed by enantioselective CH amination reaction can have the structure of Formula VII:

    ##STR00039## [0139] wherein R.sub.15-R.sub.20 can be independently hydrogen, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C.sub.1-C.sub.10 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.8 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.6 linear or branched alkyl, etc.), a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a halide, a hydroxyl, a carbonyl, an amino, an amido, a silyl, or a siloxyl, or R.sub.20 and R.sub.15 together or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, can form a substituted or unsubstituted cycloalkyl (including monocyclic, such as a substituted or unsubstituted cyclopentyl and cyclohexyl, and polycyclic, such as a substituted or unsubstituted fused cycloalkyl ring), a substituted or unsubstituted cycloalkenyl (monocyclic or polycyclic, such as a fused cycloalkenyl ring), a substituted or unsubstituted cycloalkynyl (monocyclic or polycyclic, such as a fused cycloalkynyl ring), a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted oxanyl, a substituted or unsubstituted thianyl, a substituted or unsubstituted oxolanyl, a substituted or unsubstituted thiolanyl, etc.), a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted heteropolyaryl; the substituents, when present, can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a siloxy, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof, such as a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a carbonyl, an oxo, an amino, or an alkoxyl; and R can be any one of those described above for RNH.sub.2 or RIN-R, such as Tces, Ts, Ns, or o/p/m-halobenzene sulfonyl or sulfonate (such as a p-chlorobenzene sulfonyl or p-chlorobenzene sulfonate).

    [0140] In some forms, R.sub.19 can be hydrogen and R.sub.20 can be a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C.sub.1-C.sub.10 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.8 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.6 linear or branched alkyl, etc.), or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, can form a substituted or unsubstituted cycloalkyl (including monocyclic, such as a substituted or unsubstituted cyclopentyl and cyclohexyl, and polycyclic, such as a substituted or unsubstituted fused cycloalkyl ring) or a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted oxanyl, a substituted or unsubstituted thianyl, a substituted or unsubstituted oxolanyl, a substituted or unsubstituted thiolanyl, etc.). In these forms, R.sub.15-R.sub.18 can be independently hydrogen, a halide, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C.sub.1-C.sub.10 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.8 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.6 linear or branched alkyl, etc.), a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a carbonyl, or a siloxyl. For example, R.sub.15, R.sub.16, and R.sub.18 are hydrogen and R.sub.17 is independently hydrogen, a halide, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C.sub.1-C.sub.10 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.8 linear or branched alkyl, a substituted or unsubstituted C.sub.1-C.sub.6 linear or branched alkyl, etc.), a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a carbonyl, or a siloxyl.

    [0141] In some forms of Formula VI and VII, R.sub.17 and R.sub.20 can be independently hydrogen, a substituted or unsubstituted alkyl (e.g., an unsubstituted C.sub.1-C.sub.10, C.sub.1-C.sub.8, or C.sub.1-C.sub.6 linear or branched alkyl), a carbonyl, an alkoxyl (e.g., methoxy, ethoxy, aryloxy, benzoether, etc.), a substituted or unsubstituted alkylaryl (e.g. benzyl), a haloalkyl, or a halide (e.g., fluoride, chloride, bromide, or iodide). In some forms of Formula VI and VII, R.sub.20 and R.sub.15 together or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, can form a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted heteroaryl, such as an unsubstituted C.sub.3-C.sub.6 cycloalkyl or an unsubstituted C.sub.3-C.sub.6 heterocycloalkyl, e.g., piperidine, piperazine, tetrahydropyran, 1,4-dioxane, thiane, 1,3-dithiane, 1,4-dithiane, morpholine, or thiomorpholine.

    [0142] In some forms, for any one of RH, RNHR, Formula VI, and Formula VII, the substituents can be independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted heterocyclyl, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted alkylaryl (e.g. benzyl), a carbonyl (e.g. carboxyl, ester, etc.), an alkoxy (e.g. methoxy, ethoxy, aryloxy, benzoether, etc.), an oxo, an amino, a halide, a hydroxyl, or a haloalkyl, or a combination thereof.

    [0143] For any one of RH, RNHR, Formula VI, and Formula VII, the alkyl can be a linear alkyl, a branched alkyl, or a cyclic alkyl (either monocyclic or polycyclic). The terms cyclic alkyl and cycloalkyl are used interchangeably herein. Exemplary alkyl include a linear C.sub.1-C.sub.30 alkyl, a branched C.sub.4-C.sub.30 alkyl, a cyclic C.sub.3-C.sub.30 alkyl, a linear C.sub.1-C.sub.20 alkyl, a branched C.sub.4-C.sub.20 alkyl, a cyclic C.sub.3-C.sub.20 alkyl, a linear C.sub.1-C.sub.10 alkyl, a branched C.sub.4-C.sub.10 alkyl, a cyclic C.sub.3-C.sub.10 alkyl, a linear C.sub.1-C.sub.6 alkyl, a branched C.sub.4-C.sub.6 alkyl, a cyclic C.sub.3-C.sub.6 alkyl, a linear C.sub.1-C.sub.4 alkyl, cyclic C.sub.3-C.sub.4 alkyl, such as a linear C.sub.1-C.sub.10, C.sub.1-C.sub.9, C.sub.1-C.sub.8, C.sub.1-C.sub.7, C.sub.1-C.sub.6, C.sub.1-C.sub.5, C.sub.1-C.sub.4, C.sub.1-C.sub.3, or C.sub.1-C.sub.2 alkyl group, a branched C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, or C.sub.3-C.sub.4 alkyl group, or a cyclic C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, or C.sub.3-C.sub.4 alkyl group. The cyclic alkyl can be a monocyclic or polycyclic alkyl, such as a C.sub.4-C.sub.30, C.sub.4-C.sub.25, C.sub.4-C.sub.20, C.sub.4-C.sub.18, C.sub.4-C.sub.16, C.sub.4-C.sub.15, C.sub.4-C.sub.14, C.sub.4-C.sub.13, C.sub.4-C.sub.12, C.sub.4-C.sub.10, C.sub.4-C.sub.9, C.sub.4-C.sub.8, C.sub.4-C.sub.7, C.sub.4-C.sub.6, or C.sub.4-C.sub.5 monocyclic or polycyclic alkyl group.

    [0144] For any one of RH, RNHR, Formula VI, and Formula VII, the alkenyl can be a linear alkenyl, a branched alkenyl, or a cyclic alkenyl (either monocyclic or polycyclic). The terms cyclic alkenyl and cycloalkenyl are used interchangeably herein. Exemplary alkenyl include a linear C.sub.2-C.sub.30 alkenyl, a branched C.sub.4-C.sub.30 alkenyl, a cyclic C.sub.3-C.sub.30 alkenyl, a linear C.sub.2-C.sub.20 alkenyl, a branched C.sub.4-C.sub.20 alkenyl, a cyclic C.sub.3-C.sub.20 alkenyl, a linear C.sub.2-C.sub.10 alkenyl, a branched C.sub.4-C.sub.10 alkenyl, a cyclic C.sub.3-C.sub.10 alkenyl, a linear C.sub.2-C.sub.6 alkenyl, a branched C.sub.4-C.sub.6 alkenyl, a cyclic C.sub.3-C.sub.6 alkenyl, a linear C.sub.2-C.sub.4 alkenyl, cyclic C.sub.3-C.sub.4 alkenyl, such as a linear C.sub.2-C.sub.10, C.sub.2-C.sub.9, C.sub.2-C.sub.8, C.sub.2-C.sub.7, C.sub.2-C.sub.6, C.sub.2-C.sub.5, C.sub.2-C.sub.4, C.sub.2-C.sub.3, C.sub.2 alkenyl group, a branched C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkenyl group, or a cyclic C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkenyl group. The cyclic alkenyl can be a monocyclic or polycyclic alkenyl, such as a C.sub.4-C.sub.30, C.sub.4-C.sub.25, C.sub.4-C.sub.20, C.sub.4-C.sub.18, C.sub.4-C.sub.16, C.sub.4-C.sub.15, C.sub.4-C.sub.14, C.sub.4-C.sub.13, C.sub.4-C.sub.12, C.sub.4-C.sub.10, C.sub.4-C.sub.9, C.sub.4- C.sub.8, C.sub.4-C.sub.7, C.sub.4-C.sub.6, or C.sub.4-C.sub.5 monocylcic or polycyclic alkenyl group.

    [0145] For any one of RH, RNHR, Formula VI, and Formula VII, the alkynyl can be a linear alkynyl, a branched alkynyl, or a cyclic alkynyl (either monocyclic or polycyclic). The terms cyclic alkynyl and cycloalkynyl are used interchangeably herein. Exemplary alkynyl include a linear C.sub.2-C.sub.30 alkynyl, a branched C.sub.4-C.sub.30 alkynyl, a cyclic C.sub.3-C.sub.30 alkynyl, a linear C.sub.2-C.sub.20 alkynyl, a branched C.sub.4-C.sub.20 alkynyl, a cyclic C.sub.3-C.sub.20 alkynyl, a linear C.sub.2-C.sub.10 alkynyl, a branched C.sub.4-C.sub.10 alkynyl, a cyclic C.sub.3-C.sub.10 alkynyl, a linear C.sub.2-C.sub.6 alkynyl, a branched C.sub.4-C.sub.6 alkynyl, a cyclic C.sub.3-C.sub.6 alkynyl, a linear C.sub.2-C.sub.4 alkynyl, cyclic C.sub.3-C.sub.4 alkynyl, such as a linear C.sub.2-C.sub.10, C.sub.2-C.sub.9, C.sub.2-C.sub.8, C.sub.2-C.sub.7, C.sub.2-C.sub.6, C.sub.2-C.sub.5, C.sub.2-C.sub.4, C.sub.2-C.sub.3, C.sub.2 alkynyl group, a branched C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkynyl group, or a cyclic C.sub.3-C.sub.9, C.sub.3-C.sub.9, C.sub.3-C.sub.8, C.sub.3-C.sub.7, C.sub.3-C.sub.6, C.sub.3-C.sub.5, C.sub.3-C.sub.4 alkynyl group. The cyclic alkynyl can be a monocyclic or polycyclic alkynyl, such as a C.sub.4-C.sub.30, C.sub.4-C.sub.25, C.sub.4-C.sub.20, C.sub.4-C.sub.18, C.sub.4-C.sub.16, C.sub.4-C.sub.15, C.sub.4-C.sub.14, C.sub.4-C.sub.13, C.sub.4-C.sub.12, C.sub.4-C.sub.10, C.sub.4-C.sub.9, C.sub.4- C.sub.8, C.sub.4-C.sub.7, C.sub.4-C.sub.6, or C.sub.4-C.sub.5 monocyclic or polycyclic alkynyl group.

    [0146] It is understood that any of the exemplary alkyl, alkenyl, and alkynyl groups can be heteroalkyl, heteroalkenyl, and heteroalkynyl, respectively.

    [0147] For any one of RH, RNHR, Formula VI, and Formula VII, the aryl group can be a C.sub.5-C.sub.30 aryl, a C.sub.5-C.sub.20 aryl, a C.sub.5-C.sub.12 aryl, a C.sub.5-C.sub.11 aryl, a C.sub.5-C.sub.9 aryl, a C.sub.6-C.sub.20 aryl, a C.sub.6-C.sub.12 aryl, a C.sub.6-C.sub.11 aryl, or a C.sub.6-C.sub.9 aryl. It is understood that the aryl can be a heteroaryl, such as a C.sub.5-C.sub.30 heteroaryl, a C.sub.5-C.sub.20 heteroaryl, a C.sub.5-C.sub.12 heteroaryl, a C.sub.5-C.sub.11 heteroaryl, a C.sub.5-C.sub.9 heteroaryl, a C.sub.6-C.sub.30 heteroaryl, a C.sub.6-C.sub.20 heteroaryl, a C.sub.6-C.sub.12 heteroaryl, a C.sub.6-C.sub.11 heteroaryl, or a C.sub.6-C.sub.9 heteroaryl. For any of Formulae I, Ia, II, III, and IV, the polyaryl group can be a C.sub.10-C.sub.30 polyaryl, a C.sub.10-C.sub.20 polyaryl, a C.sub.10-C.sub.12 polyaryl, a C.sub.10-C.sub.11 polyaryl, or a C.sub.12-C.sub.20 polyaryl. It is understood that the aryl can be a polyheteroaryl, such as a C.sub.10-C.sub.30 polyheteroaryl, a C.sub.10-C.sub.20 polyheteroaryl, a C.sub.10-C.sub.12 polyheteroaryl, a C.sub.10-C.sub.11 polyheteroaryl, or a C.sub.12-C.sub.20 polyheteroaryl.

    [0148] In some forms of the method, the substrate used in the enantioselective CH amination reaction can have a structure of any one of the following:

    ##STR00040## ##STR00041##

    and the aminated product can have a structure of any one of the following:

    ##STR00042## ##STR00043## ##STR00044##

    [0149] Generally, the substrate and the nitrogen-source reactant in the reaction mixture of the disclosed method can have a molar ratio in a range from 10:1 to 1:1 or from 10:1 to 5:1, such as 8:1.

    [0150] Exemplary solvents suitable for use in forming the reaction mixture containing the substrate, the nitrogen-source reactant, the catalytic system disclosed herein, and the solvent include, but are not limited to, CH.sub.3CN, THF, HFIP, and C.sub.6H.sub.6. For example, the solvent forming the reaction mixture is CH.sub.3CN.

    [0151] In some forms, the reaction mixture of the disclosed method further contains a drying agent, such as MgO, or a molecular sieve, such as a 3 molecular sieve, a 4 molecular sieve, or a 5A molecular sieve, or a combination thereof. The use of a drying agent and/or a molecular sieve in the reaction mixture can remove residue moisture in the reaction mixture.

    [0152] The reaction conditions for performing the enantioselective CH amination reactions, such as reaction time, gas environment, stirring, etc., depend on the specific reactants and desired products of the reactions. For example, the CH amination catalyzed by the catalytic system disclosed herein is performed at room temperature for a period of time in a range from about 30 minutes to about 24 hours, from about 1 hour to about 20 hours, or from about 2 hours to about 18 hours, such as about 16 hours, and optionally under an inert gas environment (such as under nitrogen, helium, and/or argon) and/or with stirring.

    [0153] Optionally, the methods for catalyzing enantioselective CH amination disclosed herein further includes a step of mixing the substrate, the nitrogen-source reactant, the disclosed catalytic system, and the solvent to form the reaction mixture prior to step (i), and/or a step of purifying the aminated product, optionally by column chromatography, subsequent to step (i).

    [0154] In some forms, the aminated product formed from the enantioselective CH amination reaction catalyzed by the catalytic system disclosed herein can have a yield of at least 30%, at least 40%, at least 50%, in a range from about 30% to about 70%, from about 40% to about 70%, or from about 50% to about 70%.

    [0155] In some forms, the aminated product formed from the enantioselective CH amination reaction catalyzed by the catalytic system disclosed herein can have an enantiomeric ratio of at least 2:1, such as in a range from 2:1 to 99:1, from 4:1 to 99:1, from 9:1 to 99:1, or from 19:1 to 99:1, as determined by chiral HPLC.

    [0156] In some forms, the aminated product formed from the enantioselective CH amination reaction catalyzed by the catalytic system disclosed herein can have a yield of at least 30%, at least 40%, at least 50%, in a range from about 30% to about 70%, from about 40% to about 70%, or from about 50% to about 70%; and an enantiomeric ratio of at least 2:1, such as in a range from 2:1 to 99:1, from 4:1 to 99:1, from 9:1 to 99:1, or from 19:1 to 99:1, as determined by chiral HPLC.

    [0157] Specific exemplary substrates, nitrogen-source reactants, and their corresponding yields and enantiomeric ratios, are described in the Examples below.

    [0158] The disclosed compositions and methods can be further understood through the following numbered paragraphs. [0159] 1. A host catalyst having a structure of:

    ##STR00045## [0160] wherein: [0161] (i) each occurrence of A, together with the carbon atoms to which it is attached, forms a crown ether; [0162] (ii) each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aralkyl, a halide, a hydroxyl, an alkoxyl, an amino, an amido, a carbonyl, a nitro, a nitrile, or a thiol; and [0163] (iii) the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof. [0164] 2. The host catalyst of paragraph 1, wherein each occurrence of A, together with the carbon atoms to which it is attached, forms a 12-crown-4 ether, a 15-crown-5-ether, an 18-crown-6 ether, a dibenzo-18-crown-6 ether, a 24-crown-8 ether, or an aza-crown ether. [0165] 3. The host catalyst of paragraph 1 or 2, wherein the host catalyst has a structure of:

    ##STR00046## [0166] 4. The host catalyst of any one of paragraphs 1-3, wherein each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a hydroxyl, an alkoxyl, or a carbonyl. [0167] 5. The host catalyst of any one of paragraphs 1-4, wherein each occurrence of R.sub.1 and R.sub.2 are hydrogen. [0168] 6. A guest template having a structure of:

    ##STR00047## [0169] wherein: [0170] (i) B.sub.1 and B.sub.2 are independently absent, a carbon atom, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; [0171] (ii) R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; [0172] (iii) ------ is absent or a bond (single, double, or triple); [0173] (iv) X.sub.1 and X.sub.2 are independently absent, oxygen atom, or NR.sub.5, and R.sub.5 is absent, hydrogen, or a substituted or unsubstituted alkyl;

    ##STR00048## [0174] (v) L.sub.1 and L.sub.2 are independently absent or [0175] X.sub.3 is a nitrogen atom or CR.sub.6, R.sub.6 is hydrogen or a substituted or unsubstituted alkyl, [0176] Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, or a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl; [0177] (vi) n.sub.1 and n.sub.2 are independently an integer from 0 to 20; and [0178] (vii) the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, an carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof. [0179] 7. The guest template of paragraph 6, wherein B.sub.1 and B.sub.2 are independently a carbon atom, a substituted or unsubstituted aryl, or a substituted or unsubstituted polyaryl; and R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted aralkyl. [0180] 8. The guest template of paragraph 6 or 7, wherein

    ##STR00049##

    is:

    ##STR00050## [0181] X.sub.1 and X.sub.2 are independently an oxygen atom or NR.sub.5, R.sub.5 is absent or hydrogen; [0182] n.sub.4 and n.sub.5 are independently an integer from 0 to 5; [0183] n.sub.6, n.sub.7, n.sub.8, and n.sub.10 are independently an integer from 0 to 4; [0184] n.sub.9 and n.sub.11 are independently an integer from 0 to 2; [0185] n.sub.12-n.sub.14 are independently an integer from 1 to 6; and [0186] R.sub.7-R.sub.14 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic. [0187] 9. The guest template of any one of paragraphs 6-8, wherein L.sub.1 and L.sub.2 are independently

    ##STR00051##

    wherein X.sub.3 is a nitrogen atom, and wherein Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl. [0188] 10. The guest template of any one of paragraphs 6-9, wherein Q.sub.1 and Q.sub.2 are unsubstituted phenyl. [0189] 11. A catalytic system comprising: [0190] a host catalyst; and [0191] a guest template, [0192] wherein the host catalyst has the structure of:

    ##STR00052## [0193] wherein: [0194] (i) each occurrence of A, together with the carbon atoms to which it is attached, forms a crown ether; [0195] (ii) each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic, a substituted or unsubstituted aralkyl, a halide, a hydroxyl, an alkoxyl, an amino, an amido, a carbonyl, a nitro, a nitrile, or a thiol; and [0196] wherein the guest template has the structure of:

    ##STR00053## [0197] wherein: [0198] (i) B.sub.1 and B.sub.2 are independently absent, a carbon atom, a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; [0199] (ii) R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic; [0200] (iii) custom-character is absent or a bond (single, double, or triple); [0201] (iv) X.sub.1 and X.sub.2 are independently absent, oxygen atom, or NR.sub.5, and R.sub.5 is absent, hydrogen, or a substituted or unsubstituted alkyl;

    ##STR00054## [0202] (v) L.sub.1 and L.sub.2 are independently absent or [0203] X.sub.3 is a nitrogen atom or CR.sub.6, R.sub.6 is hydrogen or a substituted or unsubstituted alkyl, [0204] Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, or a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl; [0205] (vi) n.sub.1 and n.sub.2 are independently an integer from 0 to 20; and [0206] wherein the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, an carboxyl, an amino, an amido, an oxo, a silyl, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof. [0207] 12. The catalytic system of paragraph 11, wherein the host catalyst and the guest template have a molar ratio ranging from 1:10 to 1:1, from 1:5 to 1:1, such as 1:2. [0208] 13. The catalytic system of paragraph 11 or 12, wherein the host catalyst and the guest template are non-covalently bound to each other, optionally via the crown ether of the host catalyst and the ammonium group of the guest template. [0209] 14. The catalytic system of paragraph 13, wherein the binding between the host catalyst and the guest template has a log (K) of at least 4.0, such as in a range from 4.0 to about 8.0 or from 4.0 to about 6.0. [0210] 15. The catalytic system of paragraph 13 or 14, wherein the host catalyst and the guest template form a structure of:

    ##STR00055## [0211] 16. The catalytic system of any one of paragraphs 11-15, wherein the host catalyst has the structure of:

    ##STR00056## [0212] 17. The catalytic system of any one of paragraphs 11-16, wherein each occurrence of R.sub.1 and R.sub.2 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a hydroxyl, an alkoxyl, or a carbonyl. [0213] 18. The catalytic system of any one of paragraphs 11-17, wherein each occurrence of R.sub.1 and R.sub.2 are hydrogen. [0214] 19. The catalytic system of any one of paragraphs 11-18, wherein B.sub.1 and B.sub.2 are independently a carbon atom, a substituted or unsubstituted aryl, or a substituted or unsubstituted polyaryl; and R.sub.3 and R.sub.4 are independently absent, hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted aralkyl. [0215] 20. The catalytic system of any one of paragraphs 11-19, wherein

    ##STR00057##

    is:

    ##STR00058## [0216] X.sub.1 and X.sub.2 are independently an oxygen atom or NR.sub.5, R.sub.5 is absent or hydrogen; [0217] n.sub.4 and n.sub.5 are independently an integer from 0 to 5; [0218] n.sub.6, n.sub.7, n.sub.8, and n.sub.10 are independently an integer from 0 to 4; [0219] n.sub.9 and n.sub.11 are independently an integer from 0 to 2; [0220] n.sub.12-n.sub.14 are independently an integer from 1 to 6; and [0221] R.sub.7-R.sub.14 are independently hydrogen, a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl, a substituted or unsubstituted aralkyl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, or a substituted or unsubstituted heterocyclic. [0222] 21. The catalytic system of any one of paragraphs 11-20, wherein L.sub.1 and L.sub.2 are independently

    ##STR00059##

    wherein X.sub.3 is a nitrogen atom, and wherein Q.sub.1 and Q.sub.2 are independently a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted cycloalkenyl, or a substituted or unsubstituted cycloalkynyl. [0223] 22. The catalytic system of any one of paragraphs 11-21, wherein Q.sub.1 and Q.sub.2 are unsubstituted phenyl. [0224] 23. The catalytic system of any one of paragraphs 13-22, wherein the host catalyst and the guest template form a complex having a structure of:

    ##STR00060## [0225] 24. A method for asymmetric CH amination of a substrate comprising: [0226] (i) maintaining a reaction mixture at room temperature for a period of time sufficient to form a product, [0227] wherein the reaction mixture comprises the substrate, a nitrogen-source reactant, the catalytic system of any one of paragraphs 11-23, and a solvent. [0228] 25. The method of paragraph 24, wherein the nitrogen-source reactant is RNH.sub.2 or RIN-R, wherein R is SO.sub.2-R.sub.1 or SO.sub.3-R.sub.2; R.sub.1 and R.sub.2 are independently a substituted or unsubstituted phenyl or a substituted or an unsubstituted alkyl (e.g., an unsubstituted linear or branched C1-C10 alkyl, an unsubstituted linear or branched C1-C8 alkyl, an unsubstituted linear or branched C1-C6 alkyl, an unsubstituted linear or branched C1-C4 alkyl, etc., such as a tert-butyl, or a haloalkyl, such as CH.sub.2CCl.sub.3, CCl.sub.3, CH.sub.2CH.sub.2CCl.sub.3, CH.sub.2CCl.sub.2CCl.sub.3, etc.); R is a substituted or unsubstituted phenyl; and the substituents, when present, are independently an unsubstituted alkyl (e.g., any one of those described above, such as a methyl), a halide (e.g., fluoride, chloride, bromide, iodide, etc.), a nitro, a cyano, a nitrile, or a carbonyl. [0229] 26. The method of paragraph 24 or 25, wherein: [0230] the substrate has a structure of R-H, and [0231] the product has a structure of R-NHR, [0232] R is a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted tetralin, a substituted or unsubstituted indane, a substituted or unsubstituted aralkyl, etc.), a substituted or unsubstituted polyaryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted heteropolyaryl, a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted chromane, a substituted or unsubstituted isochromane, a substituted or unsubstituted thiochromane, a substituted or unsubstituted isothiochromane, dihydrobenzofuran, dihydroisobenzofuran, dihydrobenzothiophene, dihydroisobenzothiophene, etc.), a substituted or unsubstituted cycloalkyl (monocyclic or polycyclic, such as a fused cycloalkyl ring), a substituted or unsubstituted cycloalkenyl (monocyclic or polycyclic, such as a fused cycloalkenyl ring), or a substituted or unsubstituted cycloalkynyl (monocyclic or polycyclic, such as a fused cycloalkynyl ring); and [0233] the substituents are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a siloxy, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof. [0234] 27. The method of paragraph 26, wherein: [0235] the substrate has a structure of:

    ##STR00061##

    and [0236] the product has a structure of:

    ##STR00062## [0237] R.sub.15-R.sub.20 are independently hydrogen, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a halide, a hydroxyl, a carbonyl, an amino, an amido, a silyl, or a siloxyl, or R.sub.20 and R.sub.15 together or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, can form a substituted or unsubstituted cycloalkyl (including monocyclic, such as a substituted or unsubstituted cyclopentyl and cyclohexyl, and polycyclic, such as a substituted or unsubstituted fused cycloalkyl ring), a substituted or unsubstituted cycloalkenyl (monocyclic or polycyclic, such as a fused cycloalkenyl ring), a substituted or unsubstituted cycloalkynyl (monocyclic or polycyclic, such as a fused cycloalkynyl ring), a substituted or unsubstituted aryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted oxanyl, a substituted or unsubstituted thianyl, a substituted or unsubstituted oxolanyl, a substituted or unsubstituted thiolanyl, etc.), a substituted or unsubstituted heteroaryl, or a substituted or unsubstituted heteropolyaryl; the substituents, when present, are independently a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted alkynyl, a substituted or unsubstituted cyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryl, a substituted or unsubstituted heteroaryl, a substituted or unsubstituted polyaryl, a substituted or unsubstituted polyheteroaryl, a substituted or unsubstituted aralkyl, a carbonyl, a halide, a hydroxyl, a phenoxy, an aroxy, an alkylthio, a phenylthio, an arylthio, a cyano, an isocyano, an alkoxyl, a nitro, a carboxyl, an amino, an amido, an oxo, a silyl, a siloxy, a sulfinyl, a sulfonyl, a sulfonic acid, a phosphonium, a phosphanyl, a phosphoryl, a phosphonyl, or a thiol, or a combination thereof, such as a substituted or unsubstituted alkyl, a substituted or unsubstituted aryl, a carbonyl, an oxo, an amino, or an alkoxyl. [0238] 28. The method of paragraph 27, wherein R.sub.19 is hydrogen and R.sub.20 is a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), or R.sub.20 and R.sub.19 together, with the carbon atoms to which they are attached, form a substituted or unsubstituted cycloalkyl (including monocyclic, such as a substituted or unsubstituted cyclopentyl and cyclohexyl, and polycyclic, such as a substituted or unsubstituted fused cycloalkyl ring) or a substituted or unsubstituted heterocyclyl (e.g., a substituted or unsubstituted oxanyl, a substituted or unsubstituted thianyl, a substituted or unsubstituted oxolanyl, a substituted or unsubstituted thiolanyl, etc.). [0239] 29. The method of paragraph 27 or 28, wherein R.sub.15-R.sub.18 are independently hydrogen, a halide, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a carbonyl, or a siloxyl. [0240] 30. The method of any one of paragraphs 27-29, wherein R.sub.15, R.sub.16, and R.sub.18 are hydrogen and R.sub.17 is hydrogen, a halide, a substituted or unsubstituted alkyl (e.g., a substituted or unsubstituted C1-C10 linear or branched alkyl, a substituted or unsubstituted C1-C8 linear or branched alkyl, a substituted or unsubstituted C1-C6 linear or branched alkyl, etc.), a substituted or unsubstituted aryl (e.g., a substituted or unsubstituted phenyl or benzyl), an alkoxyl (e.g., a methoxyl, an ethoxyl, etc.), a carbonyl, or a siloxyl. [0241] 31. The method of any one of paragraphs 25-30, wherein R is Tces, Ts, Ns, halobenzene sulfonyl, or halobenzene sulfonate (e.g., a p-chlorobenzene sulfonyl or p-chlorobenzene sulfonate); and R is an unsubstituted phenyl or a phenyl substituted with alkyl or halide (e.g., a chlorobenzene or alkylbenzene). [0242] 32. The method of any one of paragraphs 24-31, wherein the nitrogen-source reactant in the reaction mixture is PhINTces. [0243] 33. The method of any one of paragraphs 24-32, wherein the substrate has a structure of:

    ##STR00063## ##STR00064##

    and the product has a structure of:

    ##STR00065## ##STR00066## [0244] 34. The method of any one of paragraphs 24 to 33, wherein the substrate and the nitrogen-source reactant have a molar ratio in a range from 10:1 to 1:1 or from 10:1 to 5:1, such as 8:1. [0245] 35. The method of any one of paragraphs 24 to 34, wherein the host catalyst has a loading in a range from about 5 mol % to about 30 mol % or from about 10 mol % to about mol %, such as about 15 mol %. [0246] 36. The method of any one of paragraphs 24 to 35, wherein the solvent is CH.sub.3CN, THF, HFIP, or C6H.sub.6, preferably wherein the solvent is CH.sub.3CN. [0247] 37. The method of any one of paragraphs 24-36, wherein the reaction mixture further comprises a drying agent or a molecular sieve, such as a 3 molecular sieve, a 4 molecular sieve, or a 5 molecular sieve. [0248] 38. The method of any one of paragraphs 24-37, wherein the reaction is performed under an inert gas environment, optionally wherein the inert gas is argon. [0249] 39. The method of any one of paragraphs 24-38, wherein the reaction mixture is maintained in a range from about 30 minutes to about 24 hours, from about 1 hour to about 20 hours, or from about 2 hours to about 18 hours, such as about 16 hours. [0250] 40. The method of any one of paragraphs 24-39, wherein the product has a yield of at least 30%, at least 40%, at least 50%, in a range from about 30% to about 70%, from about 40% to about 70%, or from about 50% to about 70%. [0251] 41. The method of any one of paragraphs 24-40, wherein the product has an enantiomeric ratio of at least 2:1, such as in a range from 2:1 to 99:1, from 4:1 to 99:1, from 9:1 to 99:1, or from 19:1 to 99:1, as determined by chiral HPLC.

    Examples

    Example 1: Exemplary Supramolecular Catalytic Systems for Asymmetric CH Amination of Various Substrate

    Materials and Methods

    [0252] The following commercially obtained reagents were used as received from Sigma-Aldrich, Diekmann Chemical, Bide Pharmatech Ltd., and J&K Chemicals. All catalytic amination reactions were conducted under argon with deoxygenated anhydrous solvent and 4A molecular sieves to exclude moisture. All other reactions were performed under a stream of argon gas with deoxygenated solvent, unless otherwise specified.

    [0253] Chiral high-performance liquid chromatography (HPLC) analyses were carried out using an Agilent Technologies 1260 Infinite II Series instrument equipped with DAD detectors and OD-H, AD-H, or OD-3 columns. Thin-layer chromatography (TLC) was conducted using Merck silica gel 60 F254 precoated plates (0.25 mm) and visualized with UV light, potassium permanganate, ceric ammonium molybdate, or Vanillin staining. Flash column chromatography was performed according to the method described by Still et al. (Still, W.C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923) using silica gel (230-400 mesh), unless otherwise specified.

    [0254] 1H-NMR spectra were recorded on a Bruker 400 MHz or 500 MHz spectrometer and are reported in ppm using the solvent as an internal standard (TMS at 0 ppm). Data are reported as follows: s=singlet, d=doublet, t=triplet, q=quartet, quin=quintet, m=multiplet, b=broad, app=apparent; coupling constant(s) in Hz; integration. Proton-decoupled 13C-NMR spectra were recorded on a Bruker 400 MHz or 500 MHZ spectrometer and are reported in ppm using the solvent (CDCl.sub.3) as an internal standard at 77.0 ppm.

    [0255] Low-resolution electrospray ionization-mass spectroscopy (ESI-MS) was recorded on a Finnigan LCQ quadrupole ion trap mass spectrometer (ThermoFisher Scientific), and high-resolution ESI-MS was measured on a Waters Corporation Micromass Q-TOF Premier quadrupole time-of -flight tandem mass spectrometer. MALDI-mass spectra were recorded on a Bruker ultrafleXtreme instrument equipped with built-in Flex control software, with calibration using porphyrinoid species, Sinapinic Acid, or a-Cyano-4-hydroxycinnamic acid matrices.

    [0256] Circular dichroism (CD) spectra were recorded on a Mattson Galaxy Series FTIR 5000 and are reported in terms of frequency of absorption (cm). UV spectra were recorded on an Agilent Technologies Cary 8454 and are reported in terms of absorbance and wavelength (nm); kinetics mode was applied for the detection of Fe-N intermediates.

    Results

    Design and Synthesis of the Supramolecular Catalytic System

    [0257] The supramolecular catalytic system is formed by the self-assembling of an 18-crown-6 substituted phthalocyanine host catalyst and a diammonium guest template (FIG. 1). The ligand of the host catalyst, H.sub.2(.sup.18-Crown-6PC), was synthesized according to literature procedure and characterized by 1H, 13C NMR, MALDI-TOF and UV-vis spectroscopies. Following a synthetic route similar to that reported in literature, Fe.sup.II (PC) complexes, Fe-1 and Fe-2 were prepared. Fe-1 is formed by .sup.18-Crown-6PC (bearing 18-crown-6 substituents on the phthalocyanine moieties) and Fe-2 is formed by .sup.tBuPC (bearing tert-butyl substituents on the phthalocyanine moieties). The complexes of Fe-1 and Fe-2 were characterized by 1H-NMR, MALDI-TOF and UV-vis spectroscopies which resemble those in literature. Fe-1 can be prepared at gram-scale. A chiral diammonium template with hexanoic acid linkers attached to (R)-(+)-2,2-diamino-1,1-binaphthyl (T1) and a series of Trost-ligand derived templates (T2a-T2i) were designed, synthesized and characterized by 1H, .sup.13C NMR and ESI-MS.

    Catalytic Studies

    [0258] The performance of chiral diammonium templates (30 mol %) for catalytic CH amination of tetralin (1 equiv.) was studied in anhydrous CH.sub.3CN with 15 mol % of Fe-1 as catalyst and PhINTces 1 (3 equiv.) as nitrogen source (Scheme 1). The yields and e.r. values are summarized in Table 1.

    ##STR00067##

    TABLE-US-00001 TABLE 1 Results of chiral diammonium template for asymmetric CH amination of tetralin. Host Guest Yield Entry Substrate Catalyst Template of 3a RSM e.r. 1 Tetralin 2a Fe-1 T1 53% 47% racemic 2 Tetralin 2a Fe-1 T2a 40% 60% 75:25 3 Tetralin 2a Fe-1 T2b 43% 57% 87:13 4 Tetralin 2a Fe-1 T2c 44% 56% 70:30 5 Tetralin 2a Fe-1 T2d 45% 55% 94:6 6 Tetralin 2a Fe-1 T2e 38% 62% 74:26 7 Tetralin 2a Fe-1 T2f 40% 60% 72:28 8 Tetralin 2a Fe-1 T2g 33% 67% 95:5 9 Tetralin 2a Fe-1 T2h 50% 50% 95:5 10 Tetralin 2a Fe-1 T2i 48% 52% 98:2

    [0259] The following three features of the chiral diammonium templates may affect the enantioselective of catalysis: (1) linkers of the templates, (2) chiral environment of the backbone, and (3) hydrogen-bonding motifs. Regarding the linkers of the templates, although the same chiral backbone of 1,1-binapthalene-2,2-diamine was installed on templates T1 and T2e (FIG. 2), enantioselective CH amination could only be achieved with the Trost-ligand derived T2e (FIG. 2, e.r. =74:26). Regarding the chiral environment of the backbone, for example, the modification of the chiral backbone for 1,1-diaminocyclohexane in T2a (FIG. 2, e.r. =75:25) to 1,2-diphenyl-1,2-ethylenediamne in T2b (FIG. 2, e.r. =87:13) was found to have significant effect on the enantioselectivity. Regarding the hydrogen-bonding motifs, templates T2d and T2e bear a similar structure, with only slight differences in the availability of hydrogen-bonding motifs adjacent to the chiral backbones (i.e. carboxylic esters in T2d and amides in T2e). The lack of hydrogen bond donors in T2d (FIG. 2, e.r. =94:6) may lead to a higher level of enantioselectivity than in T2e (FIG. 2, e.r. =74:26).

    [0260] For the reactivity, the product yield was impacted by the diammonium template if the size of the reaction cavity is too small (as demonstrated by T2g in FIG. 2, which is more than 10% lower in product yield than T2d, T2h and T2i). T2h was selected for further catalytic studies because of its high product yield (Table 1, product yield=50%) while retaining a high level of enantioselectivity (e.r. =94:6).

    [0261] The study of Fe-1/T2h/1 catalytic system is shown in Scheme 1 and the results are summarized in Table 2. The ratio for substrate: nitrogen source was varied (Table 2, entry 1-3, product yield=50-60%, e.r. =95:5-98:2), which showed a suitable ratio of substrate: nitrogen source being 8:1. The solvent effect (CH.sub.2C12, HFIP and THE, Table 2, entry 4-6, product yield=50-60%, e.r. =95:5-98:2) was examined. The reaction conditions of entry 3 was used except for the solvent. CH.sub.3CN as solvent gave the highest product yield (Table 2, entry 3) and is comparable to intermolecular CH amination using a known catalyst Mn(Cl.sub.8PC)Cl (Table 2, entry 9).

    TABLE-US-00002 TABLE 2 Results of Fe-1/T2h/1 catalytic system for asymmetric CH amination of tetralin. Substrate Catalyst Equiv. Yield Entry (Equiv.) (Cat. Loading) Solvent of 1 Additive of 3a .sup.a e.r..sup.b 1 Tetralin 2a (1 Fe-1 (15 mol %) CH.sub.3CN 3 N/A 50% 95:5 equiv.) 2 Tetralin 2a (5 Fe-1 (15 mol %) CH.sub.3CN 1 N/A 53% 98:2 equiv.) 3 Tetralin 2a (8 Fe-1 (15 mol %) CH.sub.3CN 1 N/A 60% 98:2 equiv.) 4 Tetralin 2a (8 Fe-1 (15 mol %) CH.sub.2Cl.sub.2 1 N/A 32% 99:1 equiv.) 5 Tetralin 2a (8 Fe-1 (15 mol %) THF 1 N/A 11% 96:4 equiv.) 6 Tetralin 2a (8 Fe-1 (15 mol %) HFIP 1 N/A 26% 95:5 equiv.) 7 Tetralin 2a (8 Fe-2 (15 mol %) CH.sub.3CN 1 N/A 76% 50:50 equiv.) 8 Tetralin 2a (8 Fe-1 (15 mol %) CH.sub.3CN 1 Ba(OTf).sub.2 60% 50:50 equiv.) (30 mol %) .sup.a Isolated yield calculated based on the ratio of conversion to product 3a: the amount of 2a; the endure yield of the reaction is remaining starting material 2a. .sup.bEnantiomeric ratio (e.r.) determined by chiral HPLC analysis. .sup.cData obtained from literature without the usage of co-catalyst template T2h.

    [0262] Two control experiments were conducted to study the effect of host-guest interactions between 18-crown-6 substituents and diammonium templates for asymmetric catalysis (Table 2, entry 7-8). Firstly, the addition of a stronger binding Ba(OTf).sub.2 additives to the Fe-1-T2h/1 catalytic system gave CH aminated product 3a with higher product yield but in a non-stereoselective manner. Secondly, replacing Fe-1 with non-18-crown-6 substituted Fe-2 resulted in non-stereoselective CH aminated product of 3a. Both results show that the host-guest interactions between 18-crown-6 substituents of Fe-1 and diammonium templates are involved in enantioselectivity catalysis.

    [0263] The amination of benzylic CH bond substrates with the Fe-1-T2h/1 catalytic system is shown in Scheme 2 and the results are summarized in Table 3. Firstly, the treatment of para-substituted ethyl benzenes 2b-f (8 equiv.) with the Fe-1 (15 mol %)/T2h (30 mol %)/1 (1 equiv.) catalytic system in CH.sub.3CN at 25 C. gave CH aminated products 3b-f with 55-70% yields and 92:8 to 96:4 e.r. (Table 3, entry 2-6). This Fe-1/T2h/1 method gave a higher product yield for substrates containing electron-donating groups (Table 3, entry 6,2f) and tolerates other organic functionalities (Table 3, entry 2-5,2b-e) with similar results as tetralin 2a). The Fe-1/T2h/1 methodology was performed at room temperature and gave CH aminated products at a relatively high level of enantioselectivity. In contrast, existing asymmetric CH amination protocols with Rh.sub.2(COOR).sub.4 as catalysts typically needs a reaction temperature of -10 to 35 C. to give a similar level of enantioselectivities.

    ##STR00068##

    TABLE-US-00003 TABLE 3 Results of Fe-1/T2h/1 catalytic system for asymmetric CH amination of various substrate. Yield Entry Substrate Product of 3a.sup.a e.r..sup.b 1 [00069]embedded image [00070]embedded image 60% 98:2 2 [00071]embedded image [00072]embedded image 56% 92:8 3 [00073]embedded image [00074]embedded image 55% 95:5 4 [00075]embedded image [00076]embedded image 56% 96:4 5 [00077]embedded image [00078]embedded image 60% 93:7 6 [00079]embedded image [00080]embedded image 70% 91:9 7 [00081]embedded image [00082]embedded image 68% 96:4 8 [00083]embedded image [00084]embedded image 65% 96:4 9 [00085]embedded image [00086]embedded image 64% 90:10 10 [00087]embedded image [00088]embedded image 60% 93:7 11 [00089]embedded image [00090]embedded image 56% 96:4 12 [00091]embedded image [00092]embedded image 50% 82:18 13 [00093]embedded image [00094]embedded image 56% 92:8 14 [00095]embedded image [00096]embedded image 61% 93:7 15 [00097]embedded image [00098]embedded image 52% 85:15 16 [00099]embedded image [00100]embedded image 50% 92:8 .sup.aIsolated yield calculated based on the ratio of conversion to product 3a-3l: the amount of 2a-2l; the endure yield of the reaction is the remaining starting materials 2a-2l. .sup.bEnantiomeric ratio (e.r.) determined by chiral HPLC analysis.

    [0264] The Fe-1/T2h/1 catalytic system can also catalyze amination of other cyclic CH bond substrates, such as indan 2g and isochroman 2h, with 65-68% yields and 96:4 e.r. (Table 3, entry 7-8, 3g-3h). For substrates containing multiple CH bonds, such as 2i-21, the Fe-1/T2h/1 catalytic system can selectively produce the benzylic CH aminated products 3i-3p with 50-64% yields and 82:18-96:4 e.r. (Table 3, entry 9-12). In contrast, literature on analogous CH functionalization via metal-carbene intermediates reported a mixture of regio-isomers for a similar diversity of substrates.

    Mechanistic Studies on CH Functionalization

    [0265] The KIE for the amination of ethylbenzene 2b with PhINTces 1 was examined by conducting competitive amination of a mixture of equimolar 2b and 2b-d.sub.10 catalyzed by Fe-1, Fe-1/T2h, or Rh.sub.2(esp).sub.2(Scheme 3). The reactions with Fe-1 and Fe-1/T2h as catalysts gave a k.sub.H/k.sub.D value of 2.6-3.0 (Table 4). This is larger than the k.sub.H/k.sub.D values obtained with Rh.sub.2(esp).sub.2 as catalyst (k.sub.H/k.sub.D=1.22, Table 4).

    ##STR00101##

    TABLE-US-00004 TABLE 4 Results of kinetic isotope experiment Entry Catalyst k.sub.H/k.sub.D 1 Fe-1 2.56 2 Fe-1/(T2h).sub.2 3.0 3 Rh.sub.2(esp).sub.2 1.22

    [0266] A tert-butyldimethylsilyl ether protected(S)-1-phenylethanol 4a was synthesized according to literature procedure. This chiral tertiary CH bond substrate was employed in the catalytic amination in CHCN.sub.3 with Fe-1 or Rh.sub.2(esp).sub.2 as catalysts at room temperature to give 4b (Scheme 4). HPLC analysis of product 4b obtained with Fe-1 as catalysts showed the racemization of the chiral CH bond center (Table 5). The chirality of 4b could be retained with Rh.sub.2(esp).sub.2 as catalysts (Table 5). This phenomenon is likely due to the generation of a short-lived organic radical during the catalytic cycle of Fe-1, which is not present in Rh.sub.2(esp).sub.2.

    ##STR00102##

    TABLE-US-00005 TABLE 5 Results of racemization of stereogenic centers experiment Entry Catalyst e.r. 1 Fe-1 50:50 2 Rh.sub.2(esp).sub.2 >99:1

    [0267] The NMR spectra of a reaction mixture of Fe-1/NH.sub.2Tces 4c with 2,4,6-trimethylpyridine 4d or PhI(OPiv).sub.2 4e were examined (FIG. 3A). The initial mixture of Fe-1/4c had no detectable paramagnetism. Following the addition of 4d or 4e, upfield chemical shifts and line broadening of the proton resonance of Fe-1 in NMR spectra were observed. Since no residual magnetic moments were detected for Fe-1/4c/4d or Fe-1/4c/4e, it is likely that the Fe-1 (NTces) species has a closed-shell character.

    [0268] Reactions of Fe-1 with 4c, 4d or 1 were monitored by UV-vis (FIG. 3B). Treatment of Fe-1 in CH.sub.3CN with 4c and 4d at room temperature resulted in an insignificant change in the UV-vis spectra. The addition of 1 to a CH.sub.3CN solution of Fe-1 resulted in prominent changes with isosbestic points. The Soret- and Q-band of Fe-1 blue shifted gradually from 418 nm to 384 nm and from 704 nm to 561 nm, respectively.

    Mechanistic Studies on the Supramolecular Aspects

    [0269] Control experiments were conducted for the catalytic CH amination of 2a with 1 as nitrogen source. These experiments employed a 1:2:4 ratio of Fe-1:T2h:Ba(OTf).sub.2 and a 1:2 ratio of Fe-2:T2h as the catalytic system (FIG. 4A). Both reactions led to the formation of aminated product 3a with a 50:50 e.r., accompanied by increased product yields. The rationale behind these non-enantioselective processes is attributed to two factors: (i) the exchange mechanism of barium cations with the ammonium templates, hence displacing the chiral supramolecular structure; and (ii) the absence of cation receptors upon substitution of the crown-ether group in the iron catalyst Fe-1 with a tert-butyl substituted in Fe-2(FIG. 4B).

    [0270] The reactions between H.sub.2(.sup.18-Crown-6PC) and templates T (i.e., T1, T2d, T2e, T2h and T2i) were monitored by .sup.1H NMR spectroscopy (FIGS. 5A and 5B). A solution of H.sub.2(.sup.18-Crown-6PC) in CD.sub.3CN was titrated with template T2d at room temperature, which resulted in a downfield shift of the 18-crown-6 signals (3.4-4.5 ppm, FIG. 5A). The shift in .sup.1H NMR signals stopped at equivalence greater than 2.0 (FIG. 5B), indicative of the H.sub.2.sup.(18-Crown-6PC):T2d=1:2 ratio for the formation of the supramolecular system H.sub.2(.sup.18-Crown-6PC)/T2d. Similar phenomena were observed for the titrations of H.sub.2(.sup.18-Crown-6PC) with T1, T2e, T2h and T2i, respectively, under the same conditions. Templates T1 and T2h in CD.sub.3CN titrated with benzo-18-crown-6 also resulted in a downfield shift of 18-crown-6 signals (3.4-4.5 ppm) and the change was halted at titrate equivalence greater than 2.0 (FIG. 5B).

    [0271] FIG. 5C shows the .sup.1H NMR spectra for the reaction between the supramolecular system H.sub.2(.sup.18-Crown-6PC)/T2h and Ba(OTf).sub.2(which has a stronger binding affinity than ammonium). The solution of H.sub.2(.sup.18-Crown-6PC)/T2h in CD.sub.3CN was titrated with Ba(OTf).sub.2, leading to: (1) upfield shift of the .sup.1H NMR signals of the NH ammonium units, (2) further downfield shift of the .sup.1H NMR signals of the crown-ether units, and (3) clearance of the aromatic signals due to reduced interactions of the aromatic groups. The changes were insignificant at titrate equivalence greater than 4.0. The titration data for supramolecular system T1, T2d, T2e, T2h and T2i are shown in FIG. 5D.

    [0272] The titration of Fe-1 in CH.sub.3CN with template T1 or T2d at room temperature was monitored by UV-vis spectroscopy (FIG. 5E). The addition of the templates led to an increase in absorbance at 300, 350 and 620 nm and a decrease in absorbance at 430 and 715 nm. The UV-vis spectra remain unchanged at an equivalence greater than 2.0. UV-vis spectra at varied temperatures (25-80 C.) of Fe-1/T1 and Fe-1/T2d in CH.sub.3CN were also conducted with no observable changes. This demonstrates that temperature has insignificant effects on the overall supramolecular structure.

    [0273] Regarding the equilibrium of the supramolecular structure, the titration data for binding between templates T1/T2h and crown-ether receptors (benzo-18-crown-6, H.sub.2(.sup.18-Crown-6PC) and Fe-1 were analyzed using BindFit under the setting of Host: Guest=1:2 (FIG. 6). Binding constants were calculated based on the change in mole fraction (which depends on the shift in .sup.1H NMR signals). The Gibbs free energies are shown in Table 6. The log (K.sub.1) and log (K.sub.2) binding constants for the benzo-18-crown-6 and T1/T2h were calculated to be 3.65/3.41 and 2.39/2.01, respectively (Table 6, entry 1-2). The binding affinities (log (K.sub.1)) and log (K.sub.2)) for the self-assembly process between H.sub.2(.sup.18-Crown-6PC) or Fe-1 and diammonium templates T1/T2h were found to be significantly larger (Table 6, entry 3-6, log (K.sub.1)=4.49-5.09 and log (K.sub.2)=4.28-5.90).

    TABLE-US-00006 TABLE 6 Binding constants between host catalyst and guest template. G.sub.K1 G.sub.K2 Entry Host Guest log(K.sub.1) (kJ/mol).sup.c log(K.sub.2) (kJ/mol).sup.c 1 T1 Benzo-18- 3.65 20.81 2.39 13.63 Crown-6 2 T2h Benzo-18- 3.41 19.44 2.01 11.46 Crown-6 3 Fe-1 T1 4.70 26.80 4.28 24.40 4 H.sub.2(.sup.18Crown6PC) T1 5.09 29.02 4.89 27.88 5 Fe-1 T2h 4.99 28.45 5.90 33.64 6 H.sub.2(.sup.18Crown6PC) T2h 4.49 25.60 5.52 31.48 .sup.aDetermined by .sup.1H-NMR titrations. .sup.bDetermined by UV-vis titrations. .sup.cCalculated from G = RTlnK, where T = 298K.

    [0274] Compared to reported host-guest catalytic systems, the log (K) for the Fe-1/T2h.sub.2 and H.sub.2(.sup.18Crown6PC)/T2h.sub.2 are 1.2-1.9 times higher than the binding of monoammonium/18-crown-6 (logK.sub.a=3.56), hydrogen bonding between two carboxylic acid groups (logK.sub.a=3.51), and anion/cyclodextrin binding (logK.sub.a=3.06). The use of diammonium templates has led to a significant improvement in binding constants compared to literature templates. The significant binding affinity of the diammonium templates may contribute to the selective asymmetric catalysis as the release of chiral diammonium templates would lead to non-stereoselective pathways.

    [0275] In view of the non-covalent interactions within the supramolecular catalysts, 2D-NMR spectroscopies (.sup.1H-.sup.1H NOSEY and .sup.1H DOSY) were applied to examine the titrates of H.sub.2(.sup.18-Crown-6PC)/T12 and H.sub.2(.sup.18-Crown-6PC)/T2h.sub.2. The .sup.1H-.sup.1H NOSEY spectra for H.sub.2(.sup.18-Crown-6PC)/T12 and H.sub.2(.sup.18-Crown-6PC)/T2h.sub.2 in CD.sub.3CN showed strong interactions between the .sup.1H resonances of the crown-ether component of H.sub.2(.sup.18-Crown-6PC) and the alkyl/aryl signals of T1/T2h at the aromatic regions (FIG. 7A). The addition of Ba(OTf).sub.2 to the CD.sub.3CN solutions of H.sub.2(.sup.18-Crown-6PC)/T12 and H.sub.2(.sup.18-Crown-6PC)/T2h.sub.2 led to significantly reduced .sup.1H-.sup.1H NOSEY NMR signals at both aromatic/crown-ether regions (FIG. 7B).

    [0276] .sup.1H DOSY NMR of H.sub.2(.sup.18-Crown-6PC)/T2h.sub.2 and Fe-1/T2h.sub.2 were conducted in CD.sub.3CN at 298 K, which showed the same diffusion coefficient of 1.09710.sup.5 cm.sup.2/s (FIG. 7C). The radius of the reaction cavity was calculated to be 5.79 by Stoke-Einstein equation.

    [0277] CD spectra of T2e and T2h were examined at variable concentrations (FIGS. 8A and 8B). For spectra of T2e, the signals at 300 nm and 385 nm gradually increased with the increase of T2e concentration, without significant changes in the shape of the signal (FIG. 8A). The addition of Fe-1 (1 equiv.) to the solution of T2e resulted in the formation of a new peak at 300 nm while the peak of Amax remained unchanged. Further addition of Ba(OTf).sub.2 to the solution of Fe-1/T2e gave a spectrum that resembled the initial spectra of T2e (without Fe-1). Similarly, CD spectra of T2h (FIG. 8B) were recorded at the same concentrations as that of T2e. By gradually diluting the solution of T2h, the recorded peak of Amax shifted within the range of +50 nm. Addition of Fe-1 and Ba(OTf).sub.2 to the diluted solution of T2h led to an insignificant change to the peak of maximum and resembled the initial spectrum of T2h, respectively (FIG. 8C). The differences in CD spectra recorded for T2e and T2h are likely due to the more pre-organized hydrogen bonding T2e scaffold, which leads to a more rigid secondary structure. The flexibility of template T2h may contribute to the highly enantioselective aminations.

    Synthesis of 4,5-dibromobenzo-18-crown-6

    ##STR00103##

    A 500 mL round-bottom flask was charged with a stir bar, 10 g (32 mmol) of benzo-18-crown-6, 0.25 g of iron powder, and dry dichloromethane. A catalytic amount of solid iodine was added at 0 C., followed by the slow addition of 3.5 mL (68.5 mmol) of bromine over a period of 2 hours. The reaction mixture was stirred for 16 hours at room temperature and then filtered into another 500 mL round-bottom flask. The resulting orange-red mixture was quenched with 100 mL of 10% aqueous sodium hydroxide. The organic layer was separated, washed with deionized water (3200 mL), dried over magnesium sulfate, and concentrated under vacuum to yield a yellow-brown oil. The oil was extracted with dry hexane (3200 mL). The combine hexane extracts were concentrated and cooled to 0 C., yielding 8 g of a colorless solid with an isolated yield of 53%.

    [0278] Appearance: White solid. .sup.1H NMR: (400 MHZ, CDCl.sub.3) 6.92(s, 2H), 4.20-3.65 (m, 20H). HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.16H.sub.22Br.sub.2O.sub.6+Na].sup.+: 490.96808, found 490.96810.

    Synthesis of 4,5-dicyanobenzo-18-crown-6

    ##STR00104##

    [0279] Under an argon atmosphere, a 500 mL round-bottom flask was equipped with a stir bar and charged with 2.52 g (5.25 mmol) of 4,5-dibromobenzo-18-crown-6, 1.43 g of copper (I) cyanide (16 mmol), and dry DMF (25 mL). The reaction mixture was heated to 150 C. for 20 hours. Subsequently, the reaction was cooled to room temperature and quenched with 100 mL of 25% aqueous ammonia. The crude product was extracted with chloroform (3200 mL). The combined organic fractions were then washed with deionized water (3200 mL), dried over magnesium sulfate, and concentrated under vacuum to obtain a brown oil. This oil was subjected to purification via column chromatography (using neutral alumina 230 mesh as the stationary phase and CHCl.sub.3 as the eluent), resulting in 1.21 g of white solid with a yield of 63%.

    [0280] Appearance: White solid. .sup.1H NMR: (300 MHz, CDCl.sub.3) 7.14 (s, 2H), 4.26-3.65 (m, 20H). HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.18H.sub.22N.sub.2O.sub.6+Na].sup.+: 362.1478, found 362.1477.

    Synthesis of Fe.SUP.(18-Crown-6.PC)

    ##STR00105##

    [0281] A 500 mL round bottom flask was charged with a stir bar, 10 g (32 mmol) of benzo-18-crown-6, 0.25 g of iron powder, and dry dichloromethane. A catalytic amount of solid iodine was added at 0 C., followed by 3.5 mL (68.5 mol) of bromine over a period of 2 hours. The reaction mixture was stirred for 16 hours at room temperature and filtered into a 500 mL round bottom flask. The resulting orange-red mixture was quenched with 100 mL of 10% aqueous sodium hydroxide. The organic layer was separated, washed with deionized water (3200 mL), dried over magnesium sulfate, and concentrated under vacuum to a yellow-brown oil. The oil was extracted with dry hexane (3200 mL). The combined hexane extracts were concentrated and cooled to 0 C., give 8 g of colorless solid with an isolated yield of 53%.

    [0282] Appearance: Dark green solid. MS: (MALDI-TOF MS+) m/z calculated for [C.sub.72H.sub.88FeN.sub.8O.sub.24].sup.+: 1504.5261, found 1504.5442. UV: (UV-vis) .sub.max (ACN)/nm 227 (/dm.sup.3 mol.sup.1 cm.sup.129367347), 292(21836735), 349 (1584694), 417 (10239796), 653 (8469389), 705.7 (12540816).

    Synthesis of N,N-([1,1-binaphthalene]-2,2-diyl)bis(6-bromohexanamide)

    ##STR00106##

    [0283] In a 250 mL round-bottom flask equipped with a stir bar, 2 g (7.04 mmol) of (R)-(+)-1,1-Binphthyl-2,2diamine, 2.93 g of 6-bromohexanoic acid (15 mmol), 85 mg of 4-dimethylaminopyridine (0.70 mmol), and dry dichloromethane (100 mL) were combined. Under an argon atmosphere, 3.71 g of solid N,N-dicyclohexylcarbodiimide (18 mmol) was added in one portion at 0 C. The reaction mixture was stirred for 24 hours at room temperature and then filtered. The solid residue was washed with dichloromethane, and the resulting colorless solution was concentrated under vacuum. The resulting yellow solids were purified using column chromatography, yielding 3.22 g of white solid with an isolated yield of 72%.

    [0284] Appearance: White solid. .sup.1H NMR: (300 MHz, CDCl.sub.3) 8.10 (d, J=9 Hz, 2H), 7.92(d, J=6 Hz, 2H), 7.83 (d, J=9 Hz, 2H), 7.35 (t, J=9 Hz, 2H), 7.13 (m, 2H), 6.96 (d, J=9 Hz, 2H), 2.96 (t, J=6 Hz, 4H), 1.88 (m, 4H), 1.16 (m, 8H), 0.91 (m, 4H). 13C NMR: (95 MHZ, CDCl.sub.3) 179.91., 141.3, 133.5, 127.5, 127.2, 126.9, 125.7, 121.7, 117.7, 115.8, 38.6, 33.8, 27.2, 25.0. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.32H.sub.34Br.sub.2N.sub.2O.sub.2].sup.+: 636.0987, found 636.0980.

    Synthesis of N,N-([1,1-binaphthalene]-2,2-diyl)bis(6-azidohexanamide)

    ##STR00107##

    [0285] In a 100 mL round-bottom flask equipped with a stir bar, 1 g (1.57 mmol) of N,N-([1,1-binaphthalene]-2,2-diyl)bis(6-bromohexanamide), 110 mg of sodium azide (1.65 mmol), and dimethyl sulfoxide (25 mL) were combined. The reaction mixture was stirred for 24 hours at 80 C. After cooling to room temperature, the organic phase was extracted with ethyl acetate (325 mL), and the combined organic phases were washed with distilled water, dried over magnesium sulfate, and concentrated under vacuum. This process yielded 750 mg of white solid with an isolated yield of 85%.

    [0286] Appearance: White solid. .sup.1H NMR: (400 MHZ, CDCl.sub.3) 8.20 (d, J=8 Hz, 2H), 8.03 (d, J=8 Hz, 2H), 7.95 (d, J=2 Hz, 2H), 7.46 (t, J=4, 8 Hz, 2H), 7.26 (t, J=4, 8 Hz, 2H), 7.07 (d, J=4 Hz, 2H), 3.07 (t, J=4, 8 Hz, 4H), 1.99 (t, J=4, 8 Hz, 4H), 1.33 (m, 4H), 1.23 (m, 4H), 1.01 (m, 4H). 13C NMR: (126 MHz, CDCl.sub.3) 179.7, 141.4, 133.3, 127.6, 127.2, 126.9, 125.5, 121.6, 117.7, 115.8, 50.1, 34.2, 27.2, 25.0. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.32H.sub.34N.sub.8O.sub.2].sup.+: 562.2805, found 562.2812.

    Synthesis of N,N-([1,1-binaphthalene]-2,2-diyl)bis(6-aminohexanamide)

    ##STR00108##

    [0287] A 100 mL three-necked round-bottom flask was equipped with a stir bar and charged with 500 mg (0.617 mmol) of N,N-([1,1-binaphthalene]-2,2-diyl)bis(6-azidohexanamide), along with 40 mL of ethyl acetate and 20 mL of methanol. The solution was degassed with argon for 20 minutes. To the reaction mixture, 50 mg of Pt/C was added under an argon atmosphere. The reaction mixture was then degassed with hydrogen and sealed with a hydrogen balloon. After stirring for 16 hours, the mixture was filtered through a short pad of celite and concentrated under reduced pressure. Flash column chromatography, using hexane:ethyl acetate as the eluent, was employed to purify the reaction mixture, yielding 332 mg of white solid as the product (yield=71%).

    [0288] .sup.1H NMR: (400 MHZ, CDCl.sub.3): 8.31 (m, 2H), 8.06 (d, J=4 Hz, 2H), 7.96 (d, J=4 Hz, 2H), 7.47 (t, J=4 Hz, 2H), 7.28 (m, 2H), 7.08 (d, J=8 Hz, 2H), 2.53 (t, J=4 Hz, 4H), 2.02(t, J=4 Hz, 4H), 1.28 (m, 8H), 1.03 (m, 4H). 13C NMR: (126 MHz, CDCl.sub.3) 179.5, 141.3, 133.2, 127.7, 127.2, 127.0, 125.5, 121.3, 117.7, 115.5, 42.5, 34.3, 27.0, 25.2. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.32H.sub.40N.sub.4O.sub.2].sup.+: 512.3151, found 512.3142.

    Synthesis of N-(2-(6-(14-azanyl) hexanamido)-[1,1-binaphthalen]-2-yl)-6-aminohexanamide ditetrafluoroborate

    ##STR00109##

    [0289] A 20 mL round-bottom flask was loaded with a stir bar, 100 mg (0.195 mmol) of N,N-([1,1-binaphthalene]-2,2-diyl)bis(6-aminohexanamide), 4 mL of diethyl ether, and 4 mL of dry dichloromethane. The solution was cooled and vigorously stirred at 0 C. A solution of HBF4 (0.505 mmol) in diethyl ether was added dropwise. After 30 minutes, the mixture was concentrated to approximately 1 mL and then filtered. The resulting off-white solid was washed with diethyl ether, yielding 55 mg of product (a 41% yield). .sup.1H NMR: (400 MHZ, CDCl.sub.3) 8.12(d, J=16 Hz, 2H), 8.04 (d, J=8 Hz, 2H). 7.95 (d, J=8 Hz, 2H), 7.52(t, J=8 Hz, 2H), 7.32(t, J=8 Hz, 2H), 7.02(d, J=16 Hz, 2H), 6.42(m, 2H), 2.00 (m, J=8 Hz, 8H), 1.39 (quin, J=8 Hz, 4H), 1.21 (m, 4H), 0.92 (m, 4H). 13C NMR: (126 MHz, CDCl.sub.3) 179.8, 141.3, 133.2, 127.7, 127.2, 127.0, 125.5, 121.5, 117.5, 115.5, 42.3, 34.3, 27.0, 25.2. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.32H.sub.40N.sub.4O.sub.2].sup.+: 512.3151, found 512.3156.

    Synthesis of ethyl 2-benzamidobenzoate

    ##STR00110##

    [0290] A 500 mL two-necked round bottom flask was charged with a stir bar, 10 g (60.6 mmol) of ethyl 2-aminobenzoate, and dry dichloromethane (200 mL). Under argon atmosphere, 25.8 mL of triethyl amine (182 mmol) was added at 0 C. in one potion, followed by a dropwise addition of 7.01 mL benzoyl chloride (60.6 mmol). The reaction mixture was refluxed for 16 hours at 50 C. The reaction mixture was concentrated to around 100 mL and the white solids were collected with filtration and washed with diethyl ether yielding 13.37 g of product (yield=82%).

    [0291] .sup.1H NMR: (400 MHZ, CDCl.sub.3) 8.29 (s, 1H), 8.04 (t, J=8, 16 Hz, 1H), 7.38 (m, 6H), 6.70 (m, 2H), 4.39 (q, J=8, 16 Hz, 2H), 1.45 (t, J=8 Hz, 3H). 13C NMR: (126 MHz, CDCl.sub.3) 168.76, 151.03, 138.97, 134.56, 131.69, 128.73, 127.19, 114.90, 111.72, 110.56, 60.33, 14.43. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.16H.sub.15NO.sub.3].sup.+: 269.1052, found 269.1058.

    Synthesis of ethyl 2-(N-(6-bromohexyl)benzamido)benzoate

    ##STR00111##

    [0292] A 100 mL round-bottom flask was equipped with a stir bar and charged with 2 g (7.44 mmol) of ethyl 2-benzamidobenzoate, along with dry dimethylformamide. Under an argon atmosphere, 715 mg of 50% sodium hydride (14.88 mmol) was added all at once at 0 C. The reaction mixture was stirred for 2 hours at room temperature. A solution of 1,6-dibromohexane (14.88 mmol) in dry dimethylformamide (20 mL) was slowly added to the reaction mixture at 0 C. The resulting yellow mixture was stirred overnight (16 hours). The reaction was quenched by pouring the mixture into a 1L beaker filled with ice-water. The organic phase was then extracted with ethyl acetate (200 mL3), and the combined organic phases were washed with deionized water (200 mL5). The solution was subsequently dried over magnesium sulfate and concentrated under reduced pressure. The product was obtained as a pale-yellow oil through flash column chromatography, using hexane:ethyl acetate as the eluent (Yield=1.35 g, 42%).

    [0293] .sup.1H NMR: (400 MHZ, CDCl.sub.3) 7.78 (dd, J=8 Hz, 1H), 7.40 (t, J=8 Hz, 1H), 7.24 (m, 3H), 7.13 (m, 4H), 4.32(q, J=8 Hz, 2H), 3.38 (t, J=8 Hz, 2H), 1.84 (m, 3H), 1.69 (m, 3H), 1.46 (m, 4H), 1.36 (t, J=8 Hz, 3H). 13C NMR: (126 MHz, CDCl.sub.3) 170.02, 165.64, 143.33, 136.20, 132.65, 131.66, 130.54, 129.41, 128.28, 127.56, 127.24, 61.54, 50.82, 33.83, 32.64, 27.88, 27.42, 26.24. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.22H.sub.25BrNO.sub.3].sup.+: 430.1018, found 430.1026.

    Synthesis of ethyl 2-(N-(6-azidohexyl)benzamido)benzoate

    ##STR00112##

    [0294] In a 100 mL round-bottom flask equipped with a stir bar, 500 mg (1.15 mmol) of ethyl 2-(N-(6-bromohexyl)benzamido)benzoate, 90 mg of sodium azide (1.39 mmol), and dimethyl sulfoxide (25 mL) were combined. The reaction mixture was stirred for 16 hours at 80 C. After cooling to room temperature, the organic phase was extracted with ethyl acetate (325 mL), and the combined organic phases were washed with distilled water, dried over magnesium sulfate, and concentrated under vacuum. This process yielded 408 mg of white solid with an isolated yield of 90%.

    [0295] .sup.1H NMR: (400 MHZ, CDCl.sub.3) 7.85 (d, J=8 Hz, 1H), 7.49 (t, J=8 Hz, 1H), 7.30 (m, 4H), 7.21 (m, 1H), 7.15 (t, J=8, 16 Hz, 2H), 3.51 (q, J=8 Hz, 3H), 3.29 (t, J=8 Hz, 2H), 1.72(m, 2H), 1.61 (m, 4H), 1.42(t, 4H), 1.20 (t, J=8 Hz, 3H). 13C NMR: (126 MHz, CDCl.sub.3) 171.35, 168.86, 143.00, 136.31, 132.60, 130.79, 129.15, 127.77, 127.41, 127.30, 61.41, 56.92, 50.96, 32.09, 28.38, 26.12, 25.10, 14.04. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.22H.sub.26N.sub.4O.sub.3].sup.+: 394.2005, found 394.2011.

    Synthesis of 2-(N-(6-azidohexyl)benzamido)benzoic acid

    ##STR00113##

    [0296] A 100 mL round-bottom flask was equipped with a stir bar and charged with 400 mg (1.02 mmol) of ethyl 2-(N-(6-azidohexyl)benzamido)benzoate, 121 mg of sodium hydroxide (3.06 mmol), 30 mL of ethanol, and 15 mL of deionized water. The reaction mixture was refluxed at 80 C. for three hours. Upon cooling to room temperature, 1M HCl was added to the reaction mixture to neutralize the solution to pH=6. The organic phase was extracted with ethyl acetate (325 mL), and the combined organic phases were washed with distilled water, dried over sodium sulfate, and concentrated under vacuum to yield 268 mg of colorless oil with an isolated yield of 72%.

    [0297] .sup.1H NMR: (400 MHZ, CD.sub.3OD) 7.85 (d, J=8 Hz, 1H), 7.48 (t, J=8 Hz, 1H), 7.29 (m, 4H), 7.17 (m, 3H), 3.28 (t, J=8 Hz, 2H), 1.71 (m, 2H), 1.59 (m, 3H), 1.41 (m, 5H). 13C NMR: (126 MHz, CD.sub.3OD) 171.46, 168.91, 143.02, 136.31, 132.63, 131.55, 130.79, 129.17, 128.74, 127.80, 127.43, 127.33, 50.98, 50.53, 28.40, 26.89, 26.30, 26.14. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.20H.sub.21N.sub.4O.sub.3+Na].sup.+: 388.1511, found 388.1514.

    Synthesis of N,N-(((((1S)-cyclohexane-1,2-diyl)bis(azanediyl))bis(carbonyl))bis(2,1-phenylene))bis(N-(6-azidohexyl)benzamide)

    ##STR00114##

    [0298] A 100 mL round bottom flask was charged with a stir bar, 1 g (2.73 mmol) of 2-(N-(6-azidohexyl)benzamido)benzoic acid, 140 mg of (1S,2S)-()-1,2-Diaminocyclohexane (1.23 mmol), 166 mg of 4-dimethylaminopyridine and dry dichloromethane (50 mL). Under argon atmosphere, 0.5 g of 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide (3.28 mmol) was added in one potion. The reaction mixture was stirred for 16 hours at room temperature. The solution was evaporated and the product was purified using column chromatography to give 1.77 g of pale yellow oil with an isolated yield of 80%.

    [0299] .sup.1H NMR: (400 MHZ, CDCl.sub.3) 7.54 (s, 1H), 7.45 (m, 5H), 7.35 (m, 2H), 7.29 (s, 1H), 7.16 (d, J=8 Hz, 2H), 7.09 (t, J=4, 8 Hz, 4H), 6.99 (m, 1H), 6.84 (d, J=8 Hz, 2H), 6.74 (d, J=4 Hz, 0.5H), 6.33 (d, J=8 Hz, 0.5H), 4.36 (q, J=4, 8 Hz, 1H), 4.25 (m, 1H), 4.05 (brs, 1H), 3.90 (m, 2H), 3.32(brs, 1H), 3.25 (m, 6H), 2.21 (m, 1H), 2.02(m, 1H), 1.84 (m, 2H), 1.70 (m, 2H), 1.56 (m, 6H), 1.37 (m, 12H). 13C NMR: (126 MHZ, CDCl.sub.3) 170.2, 167.6, 142.2, 141.4, 136.4, 135.9, 134.5, 132.9, 131.3, 130.9, 129.5, 128.7, 128.5, 127.6, 127.5, 126.9, 126.0, 54.4, 45.6, 42.0, 33.5, 32.3, 31.6, 29.7, 27.4, 26.8, 26.0, 25.0, 24.8, 22.7, 17.0, 14.1. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.46H.sub.54N.sub.10O.sub.4].sup.+: 810.4330, found 810.4336.

    Synthesis of N,N-(((((IR)-cyclohexane-1,2-diyl)bis(azanediyl))bis(carbonyl))bis(2,1-phenylene))bis(N-(6-aminohexyl)benzamide)

    ##STR00115##

    [0300] A 100 mL three-necked round-bottom flask was equipped with a stir bar and charged with 500 mg (0.617 mmol) of N,N-(((((1S)-cyclohexane-1,2-diyl)bis(azanediyl))bis(carbonyl))bis(2,1-phenylene))bis(N-(6-azidohexyl)benzamide), along with 40 mL of ethyl acetate and 20 mL of methanol. The solution was degassed with argon for 20 minutes. To the reaction mixture, 50 mg of Pt/C was added under an argon atmosphere. The reaction mixture was then degassed with hydrogen and sealed with a hydrogen balloon. After stirring for 16 hours, the mixture was filtered through a short pad of celite and concentrated under reduced pressure. Flash column chromatography, using hexane:ethyl acetate as the eluent, was employed to purify the reaction mixture, yielding 332 mg of white solidas the product (yield=71%).

    [0301] .sup.1H NMR: (400 MHZ, CDCl.sub.3) 7.45 (m, 8H), 7.12(m, 8H), 6.84 (m, 2H), 4.39 (m, 2H), 4.22(t, J=9 Hz, 2H), 3.91 (m, 4H), 3.56 (s, 4H), 3.19 (m, 2H), 2.61 (t, J=6 Hz, 4H), 2.30 (t, J=9 Hz, 4H), 1.88 (m, 12H), 1.67 (m, 4H). 13C NMR: (126 MHZ, CDCl.sub.3) & 170.4, 167.2, 142.1, 141.6, 136.8, 136.0, 134.6, 133.0, 131.5, 130.9, 129.6, 128.9, 128.4, 127.5, 127.3, 126.8, 126.1, 45.8, 42.5, 42.3, 33.6, 32.1, 32.0, 29.6, 27.3, 26.9, 25.9, 24.9, 24.5, 22.5, 17.3, 14.5. HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.46H.sub.58N.sub.6O.sub.4].sup.+: 758.4520, found 758.4526.

    Synthesis of 6,6-((((((1R)-cyclohexane-1,2-diyl)bis(azanediyl))bis(carbonyl))bis(2,1-phenylene))bis(benzoylazanediyl))bis(hexan-1-aminium) ditetrafluoroborate

    ##STR00116##

    [0302] A 20 mL round-bottom flask was loaded with a stir bar, 200 mg (0.263 mmol) of N,N-(((((1R)-cyclohexane-1,2-diyl)bis(azanediyl))bis(carbonyl))bis(2,1-phenylene))bis(N-(6-aminohexyl)benzamide), 4 mL of diethyl ether, and 4 mL of dry dichloromethane. The solution was cooled and vigorously stirred at 0 C. A solution of HBF4 (0.605 mmol) in diethyl ether was added dropwise. After 30 minutes, the mixture was concentrated to approximately 1 mL and then filtered. The resulting off-white solid was washed with diethyl ether, yielding 61 mg of product (a 25% yield).

    [0303] .sup.1H NMR: (400 MHZ, CDCl.sub.3) 7.17 (m, 6H), 7.00 (m, 2H), 6.87 (m, 2H), 6.59 (m, 2H), 6.04 (brs, 2H), 3.99 (m, 1H), 3.84 (m, 1H), 3.72(m, 1H), 3.60 (m, 1H), 2.91 (m, 2H), 2.62(m, 4H), 2.33 (t, J=4 Hz, 2H), 2.04 (m, 2H), 1.76 (m, 2H), 1.51 (m, 2H), 1.13 (m, 16H). HRMS: (ESI-TOF MS ES+) m/z calculated for [C.sub.46H.sub.60N.sub.6O.sub.4].sup.+: 760.4676, found 760.4670.

    Self-Assembly of Fe-1 or H.SUB.2.(.SUP.18Crown6.PC)/T Supramolecular Catalysts

    [0304] A 25 mL Teflon-capped Schlenk tube was charged with the following components: complex Fe-1 or H.sub.2(.sup.18Crown6PC) (15 mg, 0.01 mmol), template T (0.01 to 0.02 mmol, 0 to 2 equiv.), and CD.sub.3CN (3 mL). The tube was placed on a stir plate and stirred vigorously at room temperature under an argon atmosphere for 30 minutes.

    [0305] .sup.1H NMR, CD, and UV-Vis spectra were recorded to determine the binding constant and the secondary supramolecular structure.

    Self-Assembly of Fe-1/T Supramolecular Catalysts

    [0306] A 25 mL Teflon-capped Schleck tube was charged with the following: complex Fe-1 (0.0375 mmol, 15 mol %), chiral template T2h (0.075 mmol, 30 mol %), substrate (0.25 mmol, 1 equiv.), CH.sub.3CN (2 mL, 0.03125 M), 4 MS (100 mg), and a magnetic stir bar. The tube was placed on a stir plate and stirred vigorously at room temperature under argon atmosphere. PhINTces (0.25 mmol, 1 equiv.) was added at one portion and the reaction turns purple within a minute. Notably, the reaction has to be conducted under argon atmosphere or would result in significant decrease in yield. After 16 hours, the solution was concentrated and the product was purified over flash column chromatography. The isolated organic product were characterized by .sup.1H NMR, .sup.13C NMR, ESI-MS and chiral HPLC.

    Evaluation of the Enantiomeric Effect of the Chiral Templates

    [0307] A 25 mL Teflon-capped Schleck tube was charged with the following components: complex Fe-1 (0.0375 mmol, 15 mol %), chiral template T2h (0.075 mmol, mol %), substrate (0.25 mmol, 1 equiv.), CH.sub.3CN (2 mL, 0.03125 M), and 4 MS (100 mg), along with a magnetic stir bar. The tube was placed on a stir plate and vigorously stirred at room temperature under an argon atmosphere. PhINTces (0.75 mmol, 3 equiv.) was added all at once, and the reaction turned purple within a minute. Importantly, the reaction had to be conducted under an argon atmosphere, as not doing so resulted in a significant decrease in yield. After 16 hours, the solution was concentrated, and the product was purified via flash column chromatography.

    [0308] The isolated organic products were characterized using .sup.1H NMR, 13C NMR, ESI-MS, and chiral HPLC. The data presented in Table 1 and FIG. 2 represent the isolated yield and the enantiomeric values determined through HPLC.

    Optimization of Condition for Amination of Tetralin

    [0309] A 25 mL Teflon-capped Schleck tube was charged with the following components: complex Fe-1 (0.0375 mmol, 15 mol %), chiral template T2h (0.075 mmol, mol %), tetralin 2a (0.25 to 2 mmol, 1 to 8 equiv.), THF or HFIP or CH.sub.2Cl.sub.2 or CH.sub.3CN (2 mL, 0.03125 M), and 4 MS (100 mg), along with a magnetic stir bar. The tube was placed on a stir plate and vigorously stirred at room temperature under an argon atmosphere. PhINTces (0.25 mmol, 1 equiv.) was added all at once, and the reaction turned purple within a minute. Importantly, the reaction had to be conducted under an argon atmosphere, as not doing so resulted in a significant decrease in yield. After 16 hours, the solution was concentrated, and the product was purified via flash column chromatography.

    [0310] The isolated organic products were characterized using .sup.1H NMR, 13C NMR, ESI-MS, and chiral HPLC. The data presented in Table 2 represent the isolated yield and the enantiomeric values determined through HPLC.

    Control Experiments for Amination of Tetralin

    [0311] A 25 mL Teflon-capped Schleck tube was charged with the following components: complex Fe-1 (0.0375 mmol, 15 mol %), chiral template T2h (0.075 mmol, mol %), tetralin 2a (0.25 to 2 mmol, 1 to 8 equiv.), THF or HFIP or CH.sub.2C.sub.12 or CH.sub.3CN (2 mL, 0.03125 M), and 4 MS (100 mg), along with a magnetic stir bar. The tube was placed on a stir plate and vigorously stirred at room temperature under an argon atmosphere. PhINTces (0.25 mmol, 1 equiv.) was added all at once, and the reaction turned purple within a minute. Importantly, the reaction had to be conducted under an argon atmosphere, as not doing so resulted in a significant decrease in yield. After 16 hours, the solution was concentrated, and the product was purified via flash column chromatography. The isolated organic products were characterized using .sup.1H NMR, .sup.13C NMR, ESI-MS, and chiral HPLC. The data presented in Table 2 represent the isolated yield and the enantiomeric values determined through HPLC.

    Evaluation of Functional Group Compatibility and Substrate Scope in Amination of benzylic sp.SUP.3 .CH Bonds

    [0312] A 25 mL Teflon-capped Schleck tube was charged with the following components: complex Fe-1 (0.0375 mmol, 15 mol %), chiral template T1-T2h (0.075 mmol, 30 mol %), substrate (2 mmol, 8 equiv.), CH.sub.3CN (2 mL, 0.03125 M), and 4 MS (100 mg), along with a magnetic stir bar. The tube was placed on a stir plate and vigorously stirred at room temperature under an argon atmosphere. PhINTces (0.25 mmol, 1 equiv.) was added all at once, and the reaction turned purple within a minute. Importantly, the reaction had to be conducted under an argon atmosphere, as not doing so resulted in a significant decrease in yield. After 16 hours, the solution was concentrated, and the product was purified via flash column chromatography.

    [0313] The isolated organic products were characterized using .sup.1H NMR, 13C NMR, ESI-MS, and chiral HPLC. The data presented in Table 3 represent the isolated yield and the enantiomeric values determined through HPLC.

    CONCLUSION

    [0314] Secondary coordination spheres as synthetic catalysts are rare. Exemplary supramolecular (host catalyst-guest template) catalytic systems with Fe-1 as host catalyst and chiral diammonium templates as guest templates were prepared and used for asymmetric CH amination of a variety of substrates. The Fe-1/T2h catalytic system is applicable to benzylic CH bond substrates with a high level of enantioselectivity and moderate product yield. The asymmetric catalysis may be attributed to the strong binding affinity of diammonium templates for the 18-crown-6 receptors, which stabilizes the overall supramolecular structure. This synthetic methodology is applicable to CH functionalization and amination reactions of a variety of substrates.

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    [0371] Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of skill in the art to which the disclosed invention belongs. Publications cited herein and the materials for which they are cited are specifically incorporated by reference. Further, unless otherwise indicated, use of the expression wt % refers to wt/wt %.

    [0372] Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Such equivalents are intended to be encompassed by the following claims.