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CHIRAL 1,3-DIARYLIMIDAZOLIUM SALT CARBENE PRECURSOR, SYNTHESIS METHOD THEREFOR, METAL SALT COMPOUND AND APPLICATION THEREOF

20200369620 ยท 2020-11-26

    Inventors

    Cpc classification

    International classification

    Abstract

    Chiral 1, 3-diarylimidazole salt carbene precursors, their methods of preparation, particularly transition metal complexes and their use in chemical synthesis are provided. In particular, an air and moisture stable chiral 1, 3-diarylimidazole carbene precursor Cu (I) complex has been prepared and applied to highly regio- and enantioselective Markovnikov hydroboration of unactivated terminal alkenes to form chiral boronic esters. Moreover, these new chiral NHCs can be potentially applied in various metal-catalyzed asymmetric transformations.

    ##STR00001##

    Claims

    1. A chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S: ##STR00175## wherein ##STR00176## is selected from the group consisting of ##STR00177## each R.sup.1 is independently selected from the group consisting of substituted or unsubstituted C.sub.1-4 alkyl, substituted or unsubstituted C.sub.3-6 cycloalkyl, or substituted or unsubstituted C.sub.1-4 alkoxy; wherein the substituent of substituted C.sub.1-4 alkyl, substituted C.sub.3-6 cycloalkyl and substituted C.sub.1-4 alkoxy is one or more selected from the group consisting of halogen, cyano, nitro, carbonyl, C.sub.1-4 alkyl, halogen-substituted C.sub.1-4 alkyl, hydroxy-substituted C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.3-6 cycloalkyl, C.sub.2-6 heterocyclic, C.sub.6-14 aryl, C.sub.2-10 heteroaryl, carboxyl or ##STR00178## when there are multiple substituents, each substituent may be the same or different; R.sup.a is C.sub.1-4 alkyl; the term C.sub.2-6 heterocyclic as used herein means C.sub.2-6 heterocyclic comprising 1-4 heteroatoms selected from the group consisting of N, O and S; the term C.sub.2-10heteroaryl as used herein means C.sub.2-10heteroaryl comprising 1-4 heteroatoms selected from the group consisting of N, O and S; each R.sup.2 is independently selected from the group consisting of C.sub.1-4 alkyl, halo, ##STR00179## or C.sub.6-14 aryl, wherein R.sup.b and R.sup.C are independently C.sub.1-4 alkyl; each R.sup.3 is independently H or C.sub.1-4 alkyl; each R.sup.4 is independently H or C.sub.1-4 alkyl; each Ar is independently C.sub.6-14 aryl or C.sub.2-10heteroaryl; or each Ar are further substituted by one or more substituents selected from the group consisting of halo, cyano, nitro, carbonyl, C.sub.1-4 alkyl, halogen-substituted C.sub.1-4 alkyl, hydroxy-substituted C.sub.1-4 alkyl, C.sub.1-4 alkoxy, C.sub.3-6 cycloalkyl, C.sub.2-6 heterocyclic, C.sub.6-14 aryl, C.sub.2-10 heteroaryl, carboxyl or ##STR00180## wherein when there are multiple substituents, each substituent may be the same or different; R.sup.a is C.sub.1-4 alkyl; the term C.sub.2-6heterocyclic as used herein means C.sub.2-6 heterocyclic comprising 1-4 heteroatoms selected from the group consisting of N, O and S; the term C.sub.2-10 heteroaryl as used herein means C.sub.2-10 heteroaryl comprising 1-4 heteroatoms selected from the group consisting of N, O and S; the term C.sub.2-10 heteroaryl as used in Ar means C.sub.2-10 heteroaryl comprising 1-4 heteroatoms selected from the group consisting of N, O and S; n is 1, 2 or 3; X is Cl.sup., Br.sup., I.sup., OTf.sup. or BF.sub.4.sup..

    2. The chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 1, wherein, each Ar is independently selected from C.sub.6-14 aryl, preferably phenyl; and/or, each Ar is further substituted by one or more from C.sub.1-4 alkyl or C.sub.1-4 alkoxy, when Ar is further substituted by one or more C.sub.1-4 alkyl, the term C.sub.1-4 alkyl is preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl; when Ar is further substituted by one or more C.sub.1-4 alkoxy, the term C.sub.1-4 alkoxy as used herein is preferably selected from the group consisting of methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy or tert-butoxy; each Ar is preferably selected from the group consisting of ##STR00181## and/or each R.sup.1 is independently C.sub.1-4 alkyl or C.sub.1-4 alkoxy, preferably methyl or methoxy; and/or each R.sup.2 is independently C.sub.1-4 alkyl, preferably methyl; and/or each R.sup.4 is independently H or methyl; and/or n is 1 or 2; and/or X is Cl.sup., Br.sup., r or BF.sub.4.sup., preferably Cl.sup. or Br; and/or each R.sup.1 are the same, each R.sup.2 are the same, each R.sup.3 are the same, and/or Ar are the same; and/or in each R.sup.1, when the substituent in substituted C.sub.1-4 alkyl, substituted C.sub.3-6 cycloalkyl and substituted C.sub.1-4alkoxy are each independently C.sub.2-10heteroaryl, the term C.sub.2-10heteroaryl as used herein refers to C.sub.3-10 heteroaryl group containing 1-4 heteroatoms selected from the group consisting of N, O and S; and/or each in R.sup.1, when the substituent in substituted C.sub.1-4 alkyl, substituted C.sub.3-6 cycloalkyl and substituted C.sub.1-4 alkoxy are each independently C.sub.2-6heterocyclic, the term C.sub.2-6heterocyclic refers to C.sub.3-10 heteroaryl group containing 1-4 heteroatoms selected from the group consisting of N, O and S. and/or in each Ar, the term C.sub.2-10heteroaryl as used refers to C.sub.5-10heteroaryl group containing 1-4 heteroatoms selected from the group consisting of N, O and S.

    3. The chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 1, wherein each Ar is independently C.sub.6-14 aryl, preferably phenyl; each R.sup.1 is independently selected from the group consisting of C.sub.1-4 alkyl or C.sub.1-4 alkoxy, preferably methyl or methoxy; each R.sup.2 is independently C.sub.1-4 alkyl, preferably methyl; each R.sup.3 is independently selected from the group consisting of H or C.sub.1-4 alkyl, preferably H or methyl; each R.sup.4 is independently selected from the group consisting of H or C.sub.1-4 alkyl, preferably H or methyl; n is 1 or 2; and/or X is Cl.sup. or Br.sup.. or Ar is independently C.sub.6-14 aryl, preferably phenyl; each R.sup.1 is independently selected from the group consisting of C.sub.1-4 alkyl or C.sub.1-4 alkoxy, preferably methyl or methoxy; each R.sup.2 is independently C.sub.1-4 alkyl, preferably methyl; each R.sup.3 is independently selected from the group consisting of C.sub.1-4 alkyl, preferably methyl; each R.sup.4 is independently selected from the group consisting of H or C.sub.1-4 alkyl, preferably H or methyl; n is 1 or 2, and/or X is Cl.sup. or Br.sup.; or ##STR00182## each Ar is independently selected from C.sub.6-14 aryl, preferably phenyl; and the Ar is further optionally substituted by one or more of C.sub.1-4 alkyl or C.sub.1-4 alkoxy; each R.sup.1 is independently selected from the group consisting of C.sub.1-4 alkyl or C.sub.1-4 alkoxy, preferably methyl or methoxy; each R.sup.3 is independently selected from the group consisting of C.sub.1-4 alkyl, preferably methyl; each R.sup.4 is independently selected from the group consisting of H or C.sub.1-4 alkyl, preferably H or methyl; n is 1 or 2, and/or X is Cl.sup. or Br.sup.. or ##STR00183## is selected from the group of ##STR00184## each Ar is independently C.sub.6-14 aryl, preferably phenyl; and the Ar is further optionally substituted by one or more selected from C.sub.1-4 alkyl or C.sub.1-4 alkoxy; each R.sup.1 is independently C.sub.1-4 alkyl, preferably methyl; each R.sup.3 is independently C.sub.1-4 alkyl, preferably methyl; each R.sup.4 is independently selected from the group consisting of H; n is 1, and/or X.sup. is Cl.sup.; or, ##STR00185## is selected from the group consisting of ##STR00186## ##STR00187## is selected from the group consisting of ##STR00188##

    4. The chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 1, which is selected from the group consisting of: ##STR00189## ##STR00190## ##STR00191##

    5. A method of preparation of the chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 1, which comprises any of the following: when R is ##STR00192## the formula S precursor is prepared by method a), which comprises reacting compounds of formula S with halomethyl alkyl ether as follows; ##STR00193## wherein ##STR00194## is ##STR00195## is ##STR00196## R.sub.1, R.sub.2, R.sub.3, R.sub.4, Ar, n and X.sup. are as defined in claim 1; or when ##STR00197## is ##STR00198## the formula S precursor is prepared by method b) which comprises the following steps: in a solvent, reacting compounds of formula M6 with S2 in the presence of base: ##STR00199## wherein ##STR00200## is selected from the ##STR00201## R.sub.1, R.sub.4, Ar, X.sup. and n are the same ones according to claim 1. X means halogen consisting of Cl, Br or I. or when ##STR00202## is ##STR00203## the formula S precursor is prepared by method c) which comprises the following steps: reacting compound of formula M8 with triethyl orthoformate with the presence of NH.sub.4X as follows: ##STR00204## wherein ##STR00205## is ##STR00206## R.sub.1, R.sub.4, Ar and X.sup. are as defined in claim 1.

    6. The method according to claim 5, wherein in method a), the reaction is conducted under solvent-free condition; and/or in method a), the halomethyl alkyl ether is chloromethyl ether and/or bromomethyl ether. and/or in method a), the molar ratio between the compound S to halomethyl alkyl ether is 1:5 to 1:30; and/or in method a), the temperature used herein is generally 80 C. to 130 C.; and/or in method b), the solvent used herein is one or more selected from the group consisting of nitrile solvents, halogenated hydrocarbon solvents, amide solvents and ether solvents; and/or in method b), the base used herein is an organic base and/or inorganic base; the organic base is preferably tertiary amine, e.g., DIPEA and/or trimethylamine; the preferable inorganic base used herein is alkali carbonate, which is one or more selected from the group consisting of Na.sub.2CO.sub.3, K.sub.2CO.sub.3 and Cs.sub.2CO.sub.3; and/or in method b), the molar ratio of base to the compound M6 is generally 0.9 to 1.5; and/or in method b), the molar ratio of the compound S2 to the compound M6 is generally 1.2 to 5; and/or in method b), the temperature used herein is 50 C. to 100 C.; and/or in method c), the formula NH.sub.4X used herein is NH.sub.4Cl or NH.sub.4Br; and/or in method c), the molar ratio of NH.sub.4X to the compound M8 is 1.2 to 3; and/or in method c), the volume molar ratio of triethyl orthoformate to the compound M8 is 3 to 15 L/mol; and/or in method c), the temperature used herein is 90 C. to 130 C.

    7. The chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 1, wherein the carbine precursor is prepared from a compound of formula M6 or M8: ##STR00207##

    8. The chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 1, wherein the copper (I) complex of 1, 3-diaryl imidazole salt carbene precursor is: ##STR00208##

    9. The chiral 1, 3-diaryl imidazole carbene precursor as shown in formula S according to claim 8, wherein the complex is compound 35: ##STR00209##

    10. The method of preparation of the complex according to claim 8, which comprises the step: in the organic solvent, reacting the chiral 1, 3-diarylimidazole carbene precursor as shown in formula S with the monovalent copper salt in the presence of a base as follows: ##STR00210## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, Ar, n and X.sup. are as defined in claim 8.

    11. The method of claim 10, wherein the organic solvent used herein is one or more low-polarity non-proton solvent selected from the group consisting of alkane solvent, arene solvent and ether solvent; the alkane solvent is preferably dichloromethane and/or hexane; the arene solvent is preferably benzene and/or toluene; the ether solvent is preferably tetrahydrofuran; the base is alkali metal tert-butoxide salts, such as sodium tert-butoxide and/or potassium t-butoxide; and/or the molar ratio of base to the 1, 3-diaryl imidazole salt carbene precursor compound represented by the formula S is 1.0 to 1.2; and/or the monovalent copper salt used herein is copper halide, such as copper (I) chloride; and/or the molar ratio of monovalent copper salt to the compound represented by the formula S used herein is preferably 0.9 to 1.2; and/or the reaction temperature is room temperature.

    12. A crystal form of compound 35, wherein when determined by single-crystal X-ray diffraction spectrum using Cu-K radiation, the crystal belongs to a hexagonal system, the space group was P6.sub.5, and the final unit cell parameters were: a=13.6295(3), =90, b=13.6295(3), =90, c=50.1903(16), =120; the volume of the unit cell (V) was 8074.4(4) 3, and the number of asymmetry units in the unit cell (Z) was 6; ##STR00211##

    13. The method of synthesizing the crystal form of compound 35 according to claim 12, wherein comprising the following steps: mixing the compound 35 with an ether solvent before filtered, and then the filtrate is placed under an atmosphere of alkane solvent; and the filtration is preferably performed after sonication; the methods of synthesizing the crystallography of compound 35 preferably comprises the following steps: a solution of compound 35 mixed with an ether solvent is filtered after sonication, and then the filtrate is placed under an atmosphere of alkane solvent; preferably, placing the filtrate under an atmosphere of alkane solvent comprises placing the filtrate in a vessel containing alkane solvent, more preferably, placing the filtrate in a wide-mouth bottle containing alkane solvent; the ether solvent used herein is one or more selected from the group consisting of isopropyl ether, methyl tert-butyl ether and diethyl ether, for example, diethyl ether; the volume mass ratio of ether solvents to the compound of 35 used herein is preferably 0.10.5 L/g; the alkane solvent is preferably selected from n-pentane and/or n-hexane.

    14. The use of copper (I) complexes of 1, 3-diaryl imidazole salt carbene precursor according to claim 8 in the asymmetric catalytic reaction, preferably hydroboration of asymmetric hydroboration of non-activated terminal olefins.

    15. The use according to claim 14, wherein, the asymmetric hydroboration of non-activated terminal olefins including the following steps: in organic solvent, with the presence of Cu (I)/chiral 1, 3-diarylimidazole carbene precursor, complex-catalyzed the asymmetric hydroboration of non-activated terminal olefins using diboron reagent with the presence of a base; more preferably, the method comprises the following steps: a) in the organic solvent, reacting copper (I) complexes of 1, 3-diaryl imidazole salt carbene precursor with diboron reagent in the presence of a base to form a mixture; b) reacting the mixture formed in step a) with non-activated terminal olefins in the presence of a proton source.

    16. The use according to claim 15, wherein in step a), the organic solvent is low-polarity non-proton solvent such as one or more of alkane solvent, arene solvent, and ether solvent; the alkane solvent is haloalkane solvent and/or unsubstituted alkane solvent, such as dichloromethane and/or hexane; the arene solvent is preferably selected from benzene and/or toluene; the ether solvent is preferably selected from tetrahydrofuran. and/or in step a), the base is alkali metal tert-butoxide salt, such as sodium tert-butoxide and/or potassium t-butoxide; and/or in step a), the molar ratio of base to the non-activated terminal olefins is 1.2 to 2; and/or in step a), the molar ratio of copper/chiral 1, 3-diarylimidazole carbene precursor complex (I) to the non-activated terminal olefin used herein is 0.01 to 0.05; and/or in step a), the diboron reagent is ##STR00212## and/or in step a), the molar ratio of diboron to the non-activated terminal olefin is 1.5 to 3. and/or in step a), the reaction temperature is room temperature. and/or in step b), the proton source is alcohol, e.g., one or more selected from the group consisting of methanol, ethanol, and isopropanol; and/or in step b), the molar ratio of proton source to the non-activated terminal olefin used herein is generally 1.5 to 3; and/or wherein step b), the reaction temperature is room temperature; and/or wherein step b), the non-activated terminal olefin used herein is of the following structure: ##STR00213## wherein Alkyl represents substituted or unsubstituted C.sub.1-10 alkyl, and the substituent of the C.sub.1-10 alkyl is one or more selected from the group consisting of halogen, C.sub.6-14 aryl, substituted C.sub.6-14 aryl, C.sub.1-10alkoxy, substituted C.sub.1-10 alkoxy, OR.sup.p1, Si(R.sup.p5).sub.3, NHC(R.sup.p6).sub.3, C.sub.2-12 heteroaryl, substituted C.sub.2-12 heteroaryl, C.sub.3-6 cycloalkyl or substituted C.sub.3-6 cycloalkyl, wherein R.sup.p1 is selected from the group consisting of C.sub.6-14 aryl, substituted C.sub.6-14 aryl, C.sub.2-12 heteroaryl, substituted C.sub.2-12 heteroaryl or SiR.sup.p4; wherein R.sup.p4 is C.sub.6-14 aryl or substituted C.sub.6-14 aryl; each R.sup.p5 and R.sup.p6 are independently C.sub.1-4 alkyl or C.sub.6-14 aryl; the substituent of the C.sub.6-14 aryl, C.sub.1-10 alkoxy, C.sub.2-12heteroaryl and C.sub.3-6 cycloalkyl is independently one or more selected from the group consisting of halo, cyano, nitro, COOR.sup.p2, C(O), C.sub.3-6 cycloalkyl, substituted C.sub.3-6 cycloalkyl, C.sub.6-14 aryl, substituted C.sub.6-14 aryl and C.sub.2-12 heteroaryl; R.sup.p2 is selected from H or C.sub.1-4alkyl; in said substituent, the substituent of C.sub.6-14 aryl is one or more selected from the group consisting of halo, SR.sup.p3, C.sub.1-4 alkyl, halogen-substituted C.sub.1-4 alkyl, C.sub.1-4 alkoxy, and halogen-substituted C.sub.1-4 alkoxy; R.sup.p3 is selected from H or C.sub.1-4 alkyl; or two adjacent substituents in the substituted C.sub.6-14 aryl together form a C.sub.2-6 heterocyclyl based on the carbons to which they are attached; the hetero atom in C.sub.2-6 heterocyclyl is 1-4 heteroatoms selected from the group consisting of N, O, and S; the substituent of substituted C.sub.3-6 cycloalkyl is one or more selected from the group consisting of C.sub.6-14 aryl or C.sub.1-4alkyl-substituted C.sub.2-12heteroaryl; the C.sub.2-12heteroaryl is a C.sub.2-12heteroaryl group comprising 1-4 heteroatoms selected from the group consisting of N, O, and S.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0191] FIG. 1 is the Single-Crystal Diffraction Patterns of (R,R,R,R)-ANIPE-CuCl (compound 35).

    DETAILED DESCRIPTION

    Example 1

    Synthesis of the 4,5-dimethyl-1,3-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium bromide (7)

    [0192] ##STR00063##

    Synthesis of the 4-methyl-2, 6-bis (1-phenylvinyl) aniline (intermediate 3)

    [0193] ##STR00064##

    [0194] A 250 mL round-bottom flask equipped with a stir bar was charged with p-methylaniline (10.7 g, 100 mmol), phenylacetylene (20.4 g, 200 mmol), and KSF montmorillonite (10 g). The flask was fitted with a reflux condenser, and the heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the red residue oil was precipitated by adding petroleum ether to give the yellow intermediate 3 (12 g, Yield=38.6%). .sup.1H NMR (CDCl.sub.3): 7.247.38 (m, 10H), 6.93 (s, 2H), 5.78 (s, 2H), 5.35 (s, 2H), 3.37 (s, 2H), 2.26 (s, 3H).

    Synthesis of the 4-methyl-2, 6-bis ((R)-1-phenylethyl) aniline (intermediate 4)

    [0195] ##STR00065##

    [0196] In a 1 L microwave tube, (NBD).sub.2RhBF.sub.4 (0.2 mol %) and (Rc, Sp)-DuanPhos (0.24 mol %) were dissolved in 40 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of intermediate 3 (1.0 equiv) in a minimal amount of DCM was added. Subsequently 400 mL MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 60 bar H.sub.2 and the mixture was stirred at ambient temperature for 48 h. The reaction mixture was suction filtered, washed with methanol, and the solid was recrystallized from methanol to afford the desired chiral white intermediate 4 (45 g, Yield=89%). .sup.1H NMR (CDCl.sub.3): 7.137.27 (m, 10H), 6.06 (s, 2H), 3.98 (q, J=8.0 Hz, 2H), 3.22 (s, 2H), 2.37 (s, 3H), 1.59 (d, J=8.0 Hz, 6H).

    Synthesis of the (2E, 3E)-N.SUP.2., N.SUP.3.-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl) butane-2, 3-diimine (intermediate 6)

    [0197] ##STR00066##

    [0198] A 100 mL round-bottom flask equipped with a stir bar was charged with 4-methyl-2, 6-bis ((R)-1-phenylethyl) aniline intermediate 4 (3 g, 9.52 mmol), 50 mL ethanol and 2, 3-butanedione 5 (432 mg, 4.76 mmol), CH.sub.3COOH (5 mol %), and the mixture was heated with vigorous stirring at 40 C. for 15 h. The reaction mixture was suction filtered, washed with ethanol, and dry to afford intermediate 6 (2.79 g, Yield=87%).

    Synthesis of the 4, 5-dimethyl-1, 3-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl)-1H-imidazol-3-ium bromide (7)

    [0199] ##STR00067##

    [0200] A 100 mL round-bottom flask equipped with a stir bar was charged with intermediate 6 (1.366 g, 2 mmol), bromomethyl ether (5 g, 40 mmol), and the mixture was heated with vigorous stirring at 100 C. for 12 h. The reaction mixture was adding ether to precipitate a white solid, suction filtered, washed with ether, and dry to afford compound 7. .sup.1H NMR (400 MHz, CDCl.sub.3) : 10.31 (s, 1H), 7.53 (s, 2H), 7.37 (s, 2H), 7.28-7.15 (m, 10H), 7.09 (s, 6H), 6.89 (s, 2H), 6.69 (d, J=6.6 Hz, 2H), 3.45 (d, J=7.5 Hz, 2H), 3.32 (d, J=6.6 Hz, 2H), 2.58 (s, 6H), 2.30 (s, 6H), 1.56 (d, J=6.4 Hz, 12H).

    Example 2

    Synthesis of the 1,3-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-3,4,5,6-tetrahydropyrimidin-1-ium iodide (compound 11)

    [0201] ##STR00068##

    Synthesis of the 1, 3-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl) urea (intermediate 8)

    [0202] ##STR00069##

    [0203] A 25 mL sealing tube equipped with a stir bar was charged with compound 4 (1.07 g, 5 mmol), DMAP (4-dimethylaminopyridine, 0.773 g, 6 mmol), DCE (dichloroethane, 10 mL) under 78 C., triphosgene was added. After rising to room temperature, the reaction mixture was heated to 80 C. After the filtration, washing twice with water, spin-drying, the residue was recrystallized from n-hexane to gave intermediate 8 (687 mg, yield=41%).

    Synthesis of the (E)-N, N-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl) formimidamide (intermediate 10)

    [0204] ##STR00070##

    [0205] A 25 mL sealing tube equipped with a stir bar was charged with compound 8 (678 mg, 1 mmol), pyridine (13 mL), aluminum oxide (1.2 g, 12 mmol), phosphorus pentoxide (2 g, 14 mmol), and the mixture was vigorous stirring at room temperature. Mixture caking, filtration and washing, spin-drying to give compound 9 as a solid which direct use for the next step.

    [0206] To compound 9 was added ethanol (12 mL), tetrahydrofuran (6 mL), and sodium borohydride (32 mg, 0.8 mmol). The mixture was vigorous stirring at room temperature for 1 h. After adding an appropriate amount of water, extraction with ethyl acetate, combining with the organic phase, spin-dry, the residue was purified by column chromatography to give the white solid compound 10 (348 mg, Yield=50%).

    Synthesis of the 1,3-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-3,4,5,6-tetrahydropyrimidin-1-ium iodide (compound 11)

    [0207] ##STR00071##

    [0208] The compound 10 (65 mg, 0.1 mmol), 1, 3-diiodopropane (88.8 mg, 0.3 mmol), DIPEA (N, N-Diisopropylethylamine, 20 uL), acetonitrile (150 uL) were charged to an 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at 80 C. for 12 h, dried in vacuo before the DCM was added, washing with saturated potassium carbonate, spin-dry to a solid, and the resultant solid was washed by adding ether to gave the white compound 11 (40 mg, Yield=38%). .sup.1H NMR (400 MHz, CDCl.sub.3) 8.46 (s, 1H), 7.31 (d, J=6.8 Hz, 9H), 7.26-7.18 (m, 7H), 7.15 (s, 5H), 6.96 (s, 2H), 6.76 (d, J=7.4 Hz, 4H), 4.29 (d, J=6.5 Hz, 2H), 3.75 (d, J=6.4 Hz, 2H), 3.55-3.43 (m, 2H), 2.82 (d, J=7.5 Hz, 2H), 2.35 (s, 7H), 1.78 (d, J=6.9 Hz, 9H), 1.14 (d, J=6.7 Hz, 6H).

    Example 3

    1, 3-Bis (4-methyl-2, 6-bis(-1-phenylethyl)phenyl)-4, 5-dihydro-1H-3-imidazolium chloride (compound 16)

    [0209] ##STR00072##

    Synthesis of the (1E, 2E)-N.SUP.1., N.SUP.2.-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl) ethane-1, 2-diimine (intermediate 14)

    [0210] ##STR00073##

    [0211] A 100 mL round-bottom flask equipped with a stir bar was charged with intermediate 4 (3 g, 9.52 mmol) was suspended in 50 mL EtOH and heated under reflux for 1 h. Drops of acetic acid (5 mol %) was then added and reflux was continued. A 40% solution of glyoxal (691 mg, 4.76 mmol) in water was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated at 40 C. for further 15 h and then cooled to room temperature. The crude product was filtered, washed with EtOH and dried in vacuo to afford the intermediate 14 as a yellow solid (2.86 g, Yield=92.1%). .sup.1HNMR (CDCl.sub.3): 7.65 (s, 2H), 7.11-7.22 (m, 20H), 6.92 (s, 4H), 4.02 (q, 0.1=8.0 Hz, 4H), 3.28 (s, 6H), 1.52 (d, 0.1=4.0 Hz, 12H).

    Synthesis of the N, N-Bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl) ethane-1, 2-diamine (intermediate 15)

    [0212] ##STR00074##

    [0213] A 100 mL round-bottom flask equipped with a stir bar was charged with compound 14 (2.86 g, 4.38 mmol), LiAlH.sub.4 (499 mg, 13.14 mmol) was suspended in 30 mL THF under a nitrogen atmosphere. The mixture was stirred at 40 C. for 12 h. Saturated KOH solution was added, and the mixture was extracted with EA for three times, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford the title product compound 15 (2.82 g, Yield=98%). .sup.1H NMR (CDCl.sub.3): 7.097.15 (m, 20H), 6.90 (s, 4H), 4.37 (q, 0.1=8.0 Hz, 4H), 2.87 (s, 2H), 2.72 (d, J=8.0 Hz, 2H), 2.49 (d, J=8.0 Hz, 2H), 2.26 (s, 6H), 1.53 (s, 12H).

    Synthesis of the 1, 3-Bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl)-4, 5-dihydro-1H-3-imidazolium chloride (compound 16)

    [0214] ##STR00075##

    [0215] A 100 mL round-bottom flask equipped with a stir bar was charged with compound 15 (2.82 g, 4.29 mmol) and NH.sub.4Cl (344 mg, 6.4 mmol) were dissolved in 20 mL HC (OEt) 3 under a nitrogen atmosphere. The mixture was stirred at 110 C. for 18 h and then cooled to room temperature. The crude product was filtered, washed with Et.sub.2O and dried in vacuo to afford the saturated imidazolium salt as a white solid compound 16 (1.81 g, Yield=60%). .sup.1H NMR (400 MHz, CDCl.sub.3) 10.32 (s, 1H), 7.38 (d, J=6.5 Hz, 3H), 7.23-7.13 (m, 4H), 6.97-6.88 (m, 3H), 4.42-4.31 (m, 1H), 4.26 (dd, J=12.9, 6.4 Hz, 1H), 3.68 (t, J=11.5 Hz, 1H), 3.03 (t, J=13.0 Hz, 1H), 2.34 (s, 3H), 1.73 (d, J=7.3 Hz, 3H), 1.44 (d, J=7.1 Hz, 3H).

    Example 4

    Synthesis of the 1, 3-Bis (4-methoxy-2, 6-bis ((R)-1-phenylethyl) phenyl)-4, 5-dihydro-1H-3-imidazolium chloride (compound 22)

    [0216] ##STR00076##

    Synthesis of the 4-Methoxy-2, 6-bis (1-phenylvinyl) aniline (intermediate 18)

    [0217] ##STR00077##

    [0218] A 250 mL round-bottom flask equipped with a stir bar was charged with p-methoxyaniline (12.316 g, 100 mmol), KSF montmorillonite (10 g), and phenylacetylene (20.4 g, 200 mmol). The flask was fitted with a reflux condenser, and the heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the residue was purified by adding petroleum ether to give intermediate 18 (10.7 g, Yield=32.7%).

    Synthesis of the 4-Methoxy-2, 6-bis ((R)-1-phenylethyl) aniline (intermediate 19)

    [0219] ##STR00078##

    [0220] In a 100 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.5 mol %) and (Rc,Sp)-DuanPhos (0.6 mol %) were dissolved in 10 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of intermediate 18 (7.36 g, 22.51 mmol) in a minimal amount of 60 mL MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 60 bar H.sub.2 and the mixture was stirred at ambient temperature for 24 h. The reaction mixture was suction filtered, washed with methanol, and the solid was recrystallized from methanol to afford the desired chiral white intermediate 19 (4.62 g, Yield=62%).

    Synthesis of the (1E, 2E)-N.SUP.1., N.SUP.2.-Bis (4-methoxy-2, 6-bis ((R) 1-phenylethyl) phenyl) ethane-1, 2-diamine (intermediate 20)

    [0221] ##STR00079##

    [0222] A 100 mL round-bottom flask equipped with a stir bar was charged with intermediate 19 (3.15 g, 9.52 mmol) was suspended in 50 mL EtOH and heated under reflux for 1 h. Drops of acetic acid (5 mol %) was then added and reflux was continued. A 40% solution of glyoxal (691 mg, 4.76 mmol) in water was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated at 40 C. for further 15 h and then cooled to room temperature. The crude product was filtered, washed with EtOH and dried in vacuo to afford the intermediate 20 as a yellow solid (2.87 g, Yield=88.1%).

    Synthesis of the N.SUP.1., N.SUP.2.-bis (4-methoxy-2, 6-bis ((R)-1-phenylethyl) phenyl) ethane-1, 2-diamine (intermediate 21)

    [0223] ##STR00080##

    [0224] A 100 mL flask equipped with a stir bar was charged with compound 20 (3 g, 4.38 mmol), LiAlH.sub.4 (499 mg, 13.14 mmol), and 30 mL THF under a nitrogen atmosphere. The mixture was stirred at 40 C. for 12 h. Saturated KOH solution was carefully added, and the mixture was extracted with EA, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford intermediate 21 (2.65 g, Yield=88%).

    Synthesis of the 1,3-Bis (4-methoxy-2,6-bis ((R)-1-phenylethyl)phenyl)-4,5-dihydro-1H-3-imidazolium chloride (compound 22)

    [0225] ##STR00081##

    [0226] To a 100 mL flask equipped with a stir bar was added intermediate 21 (2.95 g, 4.29 mmol), NE.sub.4Cl (344 mg, 6.4 mmol), and 20 mL HC(OEt).sub.3 under a nitrogen atmosphere. The mixture was stirred at 110 C. for 18 h and then cooled to room temperature. The crude product was filtered, washed with Et.sub.2O and dried in vacuo to afford compound 22 as a white solid (2.015 g, Yield=64%). .sup.1H NMR (400 MHz, CDCl.sub.3) 9.96 (s, 1H), 7.40-7.32 (m, 8H), 7.20 (t, J=7.3 Hz, 6H), 7.14 (t, J=7.2 Hz, 2H), 6.94 (s, 3H), 6.89 (d, J=2.8 Hz, 2H), 6.63 (d, J=2.8 Hz, 2H), 4.37 (q, J=7.1 Hz, 2H), 4.22 (q, J=6.8 Hz, 2H), 3.77 (s, 6H), 3.74-3.54 (m, 2H), 3.19-2.82 (m, 2H), 1.74 (t, J=10.3 Hz, 9H), 1.44 (d, J=7.0 Hz, 6H).

    Example 5

    Synthesis of the 7,9-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium chloride (compound 25)

    [0227] ##STR00082##

    Synthesis of the (1E, 2E)-N.SUP.1., N.SUP.2.-bis (4-methyl-2, 6-bis ((R)-1-phenylethyl)phenyl) acenaphthylene-1, 2-diimine (intermediate 24)

    [0228] ##STR00083##

    [0229] A 100 mL flask equipped with a stir bar was charged with compound 4 (2.52 g, 8 mmol) and acetonitrile (40 mL) and was heated under reflux (80 C.) for 1 h. Acetic acid (15 mL) was then added and reflux was continued until the mixture was completely dissolved. To this hot solution, compound 23 (770 mg, 4 mmol) was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated under reflux for a further 12 h and then cooled to room temperature. The crude product was filtered and dried in vacuo to afford the title intermediate 24 as a yellow solid (2.25 g, Yield=72.4%).

    Synthesis of the 7,9-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium chloride (compound 25)

    [0230] ##STR00084##

    [0231] Compound 24 (1.5 g, 1.93 mmol) and chloromethyl ethyl ether (3.65 g, 38.61 mmol) were added to a nitrogen-flushed thick-walled reaction vessel. The vessel was sealed and the reaction mixture was stirred at 80 C. for 24 h. The reaction mixture was cooled to ambient temperature and the resulting solid was filtered to afford the title compound 25 as a pale yellow solid (1.2 g, Yield=75.5%), .sup.1H NMR (400 MHz, CDCl.sub.3) 10.87 (s, 1H), 7.78 (d, J=8.2 Hz, 2H), 7.42-7.22 (m, 12H), 7.17 (s, 2H), 7.06 (s, 2H), 6.71 (d, J=7.0 Hz, 2H), 6.63-6.41 (m, 10H), 4.03 (dd, 0.1=13.5, 6.6 Hz, 2H), 3.70 (d, 0.1=6.2 Hz, 3H), 2.44 (s, 6H), 1.51 (d, 0.1=7.0 Hz, 6H), 1.37 (d, J=6.4 Hz, 6H).

    Example 6

    Synthesis of the 1,6-dimethyl-7,9-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium bromide (compound 28)

    [0232] ##STR00085##

    Synthesis of the (1E,2E)-3,8-dimethyl-N.SUB.1.,N.SUB.2.-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)acenaphthylene-1,2-diimine (intermediate 27)

    [0233] ##STR00086##

    [0234] A 100 mL flask equipped with a stir bar was charged with intermediate 4 (661 mg, 2.1 mmol) and acetonitrile (20 mL) and was heated under reflux (80 C.) for 1 h. Acetic acid (7 mL) was then added and reflux was continued until the mixture was completely dissolved. To this hot solution, compound 26 (200 mg, 0.95 mmol) was added, and the resulting mixture was heated under reflux for a further 36 h and then cooled to room temperature. The crude product was filtered and dried in vacuo to afford compound 27 as a purple solid (515 mg, Yield=67.4%).

    Synthesis of the 1,6-dimethyl-7,9-bis(4-methyl-2,6-bis((R)-1-phenylethyl)phenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium bromide (compound 28)

    [0235] ##STR00087##

    [0236] Compound 27 (64.4 mg, 0.08 mmol) and bromomethyl ether (151 mg, 1.6 mmol) were added to a nitrogen-flushed thick-walled reaction vessel. The vessel was sealed and the reaction mixture was stirred at 100 C. for 24 h. The reaction mixture was cooled to ambient temperature and the resulting solid was filtered off to afford the title compound 28 as a solid (42 mg, Yield=65%). .sup.1H NMR (400 MHz, dmso) 10.09 (s, 1H), 7.94 (d, J=7.7 Hz, 1H), 7.87 (t, J=7.3 Hz, 1H), 7.55 (t, J=8.2 Hz, 2H), 7.43-7.35 (m, 3H), 7.33-7.25 (m, 1H), 7.17 (d, 0.1=7.5 Hz, 2H), 6.17 (d, 0.1=16.0 Hz, 1H), 5.87 (d, 0.1=16.6 Hz, 1H), 4.82 (d, 0.1=7.0 Hz, 1H), 4.01 (d, J=6.9 Hz, 1H), 2.29 (s, 3H), 1.77 (d, J=7.0 Hz, 3H), 1.69 (d, J=7.1 Hz, 3H), 1.21 (s, 4H).

    Example 7

    Synthesis of the 1,3-bis(3,4,5-trimethyl-2,6-bis((R)-1-phenylethyl)phenyl)-4,5-dihydro-1H-imidazol-3-ium chloride (compound 34)

    [0237] ##STR00088##

    Synthesis of the 3, 4, 5-trimethyl-2, 6-bis (1-phenylvinyl) aniline (intermediate 30)

    [0238] ##STR00089##

    [0239] A 250 mL flask equipped with a stir bar was charged with 3, 4, 5-trimethylaniline (10.715 g, 100 mmol), KSF montmorillonite (10 g), and phenylacetylene (20.4 g, 200 mmol). The heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed under reduced pressure, and the residue was purified by adding petroleum ether to give intermediate 30 (10 g, Yield=30.6%).

    Synthesis of the 3, 4, 5-trimethyl-2, 6-bis ((R)-1-phenylethyl) aniline (intermediate 31)

    [0240] ##STR00090##

    [0241] In a 100 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.5 mol %) and (Rc,Sp)-DuanPhos (0.6 mol %) were dissolved in 10 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of intermediate 30 (7 g, 22.51 mmol) in a minimal amount of MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 60 bar H.sub.2 and the mixture was stirred at ambient temperature for 24 h. The reaction mixture was suction filtered, washed with methanol, and the solid was recrystallized from methanol to afford the desired chiral white intermediate 31 (4.7 g, Yield=68%).

    Synthesis of the (1E,2E)-N.SUP.1.,N.SUP.2.-bis(3,4,5-trimethyl-2,6-bis((R)-1-phenylethyl)phenyl)ethane-1,2-diimine (intermediate 32)

    [0242] ##STR00091##

    [0243] A 100 mL flask equipped with a stir bar was charged with intermediate 31 (3.15 g, 9.52 mmol) and 50 mL EtOH and was heated under reflux for 1 h. Drops of acetic acid (5 mol %) was then added and reflux was continued. A 40% solution of glyoxal (691 mg, 4.76 mmol) in water was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated at 40 C. for further 15 h and then cooled to room temperature. The crude product was filtered, washed with EtOH and dried in vacuo to afford the intermediate 32 as a yellow solid (2.1 g, Yield=81%).

    Synthesis of the N.SUP.1., N.SUP.2.-bis (3, 4, 5-trimethyl-2, 6-bis ((R)-1-phenylethyl) phenyl) ethane-1, 2-diamine (intermediate 33)

    [0244] ##STR00092##

    [0245] A 100 mL flask equipped with a stir bar was charged with intermediate 32 (3.4 g, 4.38 mmol), LiAlH.sub.4 (499 mg, 13.14 mmol), and 30 mL THF under a nitrogen atmosphere. The mixture was stirred at 40 C. for 12 h. Saturated KOH solution was added, and the mixture was extracted with ethyl acetate three times, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford t intermediate 33 (2.1 g, Yield=81%).

    Synthesis of the 1,3-bis(3,4,5-trimethyl-2,6-bis((R)-1-phenylethyl)phenyl)-4,5-dihydro-1H-imidazol-3-ium chloride (compound 34)

    [0246] ##STR00093##

    [0247] A 100 mL round-bottom flask equipped with a stir bar was charged with compound 33 (2.82 g, 4.29 mmol), NH.sub.4Cl (344 mg, 6.4 mmol), and 20 mL HC (OEt).sub.3 under a nitrogen atmosphere. The mixture was stirred at 110 C. for 18 h and then cooled to room temperature. The crude product was filtered, washed with Et.sub.2O and dried in vacuo to afford the saturated imidazolium salt as a white solid compound 34 (1.1 g, Yield=55%). .sup.1H NMR (400 MHz, CDCl.sub.3) 10.32 (s, 1H), 7.38 (d, J=6.5 Hz, 3H), 7.23-7.13 (m, 4H), 6.97-6.88 (m, 3H), 4.42-4.31 (m, 1H), 4.26 (dd, J=12.9, 6.4 Hz, 1H), 3.68 (t, J=11.5 Hz, 1H), 3.03 (t, J=13.0 Hz, 1H), 2.34 (s, 3H), 2.21 (s, 3H), 2.14 (s, 3H), 1.73 (d, J=7.3 Hz, 3H), 1.44 (d, J=7.1 Hz, 3H).

    Example 8

    Synthesis of the 1,3-bis (4-methyl-2,6-bis ((R)-1-(m-tolyl) ethyl) phenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0248] ##STR00094## ##STR00095##

    Synthesis of the 2, 6-bis (1-(3-methylphenyl) vinyl)-4-methylaniline

    [0249] ##STR00096##

    [0250] A 100 mL flask equipped with a stir bar was charged with p-methylaniline (4.3 g, 40 mmol, 1 eq.), KSF montmorillonite (4 g), and 3-methylphenylacetylene (11.4 mL, 88 mmol, 2.2 eq.). The heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the residue was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a pale yellow liquid (4.7 g, Yield=35%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.24-7.16 (m, 6H), 7.16-7.05 (m, 2H), 6.99 (s, 2H), 5.79 (d, J=1.6 Hz, 2H), 5.38 (d, J=1.6 Hz, 2H), 3.39 (s, 2H), 2.37 (s, 6H), 2.35 (s, 3H).

    Synthesis of the 2, 6-bis ((R)-1-(3-methylphenyl) ethyl)-4-methylaniline

    [0251] ##STR00097##

    [0252] In a 100 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.2 mol %) and (Rc,Sp)-DuanPhos (0.24 mol %) were dissolved in 3 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of 2, 6-bis (1-(3-methylphenyl) vinyl)-4-methylaniline (1.6 g, 4.7 mmol, 1.0 equiv) in a minimal amount of 30 mL MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 60 bar H.sub.2 and the mixture was stirred at ambient temperature for 48 h. The reaction mixture was suction filtered, washed with methanol, and the solid was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a white solid (1.5 g, Yield=93%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.19-7.13 (m, 2H), 7.10 (s, 2H), 7.03-6.95 (m, 6H), 3.98 (q, J=7.1 Hz, 2H), 3.28 (s, 2H), 2.42 (s, 3H), 2.31 (s, 6H), 1.61 (d, J=7.2 Hz, 6H).

    Synthesis of the (1E, 2E)-N.SUP.1., N.SUP.2.-bis (4-methyl-2, 6-bis ((R)-1-(m-tolyl) ethyl) phenyl) ethane-1, 2-diimine

    [0253] ##STR00098##

    [0254] A 50 mL flask equipped with a stir bar was charged with 2, 6-bis ((R)-1-(3-methylphenyl) ethyl)-4-methylaniline (687 mg, 2 mmol, 1 eq.) and 10 mL EtOH and was heated under reflux for 1 h. Drops of acetic acid (5 mol %) was then added and reflux was continued. A 40% solution of glyoxal (691 mg, 4.76 mmol) in water was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated under reflux for further 12 h and then cooled to room temperature. The concentrated crude product was used for the next step without further purification.

    Synthesis of the N.SUP.1., N.SUP.2.-bis (4-methyl-2, 6-bis ((R)-1-(m-tolyl) ethyl) phenyl) ethane-1, 2-diamine

    [0255] ##STR00099##

    [0256] A 100 mL flask equipped with a stir bar was charged with (1E, 2E)-N.sup.1, N.sup.2-bis (4-methyl-2, 6-bis ((R)-1-(m-tolyl) ethyl)phenyl) ethane-1, 2-diimine and 20 mL THF. The mixture was cooled to 0 C. before LiAlH.sub.4 (3.0 eq) was added under a nitrogen atmosphere. The mixture was stirred at 40 C. for 12 h. Saturated KOH solution was added, and the mixture was extracted with ethyl acetate, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford the title compound (570 mg, two-step total Yield=80%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.05 (t, J=7.5 Hz, 4H), 6.96 (d, J=1.9 Hz, 4H), 6.93 (d, J=6.2 Hz, 12H), 4.37 (q, J=7.1 Hz, 4H), 2.87-2.73 (m, 2H), 2.61-2.49 (m, 2H), 2.28 (s, 6H), 2.23 (s, 12H), 1.54 (d, J=7.2 Hz, 12H).

    Synthesis of the 1, 3-bis (4-methyl-2, 6-bis ((R)-1-(m-tolyl) ethyl) phenyl)-4, 5-dihydro-1H-imidazol-3-ium chloride

    [0257] ##STR00100##

    [0258] A 50 mL flask equipped with a stir bar was charged with N.sup.1, N.sup.2-bis (4-methyl-2, 6-bis ((R)-1-(m-tolyl) ethyl) phenyl) ethane-1, 2-diamine (630 mg, 0.88 mmol), NH.sub.4C.sub.1 (70.9 mg, 1.33 mmol, 1.5 eq.) and 10 mL HC (OEt).sub.3 under a nitrogen atmosphere. The mixture was stirred at 115 C. for 15 h and then cooled to room temperature. The crude product was was purified by column chromatography to afford the title saturated imidazolium salt as a white solid (415 mg, Yield=62%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 10.40 (s, 1H), 7.25 (d, J=7.5 Hz, 2H), 7.18 (d, J=14.9 Hz, 6H), 7.08 (t, J=7.5 Hz, 2H), 7.02 (d, J=7.3 Hz, 2H), 6.95 (d, J=5.9 Hz, 4H), 6.74-6.62 (m, 4H), 4.29 (q, J=6.7 Hz, 2H), 4.13 (q, J=6.5 Hz, 2H), 3.78-3.62 (m, 2H), 3.19-3.01 (m, 2H), 2.35 (s, 12H), 2.23 (s, 6H), 1.73 (d, J=7.1 Hz, 6H), 1.42 (d, J=7.0 Hz, 6H).

    Example 9

    Synthesis of the 1,3-bis(2,6-bis((R)-1-(3,5-dimethylpheny)ethyl)-4-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0259] ##STR00101## ##STR00102##

    Synthesis of the ((3, 5-dimethylphenyl) ethynyl) trimethylsilane

    [0260] ##STR00103##

    [0261] A 300 mL flask equipped with a stir bar was charged with 3, 5-dimethylbromobenzene (11.5 g, 1200 mmol), trimethylethynyl silicon (11.5 mL, 120 mmol), cuprous iodide (762 mg, 4 mmol %), bis (triphenylphosphine) palladium (II) chloride (2.344 g, 2 mmol %), and 150 mL Et.sub.3N. The mixture was stirred at 100 C. for 24 h and then cooled to room temperature. The crude product was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a pale yellow liquid (19.9 g, Yield=98.5%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.11 (s, 2H), 6.95 (s, 1H), 2.28 (s, 6H), 0.25 (s, 9H).

    Synthesis of the 3, 5-dimethylphenylacetylene

    [0262] ##STR00104##

    [0263] A 1 L flask equipped with a stir bar was charged with ((3, 5-dimethylphenyl) ethynyl) trimethylsilane (19 g, 82.6 mmol, 1.0 equiv), 250 mL MeOH, K.sub.2CO.sub.3 (17.1 g, 300 mmol). The mixture was stirred at room temperature for 12 h. The MeOH solution was removed by concentrated, diluted with ether and the mixture was washed with saturated NaCl solution, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a slightly yellow liquid (12.7 g, Yield=96.9%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.14 (s, 2H), 6.99 (s, 1H), 3.02 (s, 1H), 2.30 (s, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) : 138.0, 130.8, 129.9, 121.8, 84.1, 76.5, 21.2.

    Synthesis of the 2, 6-bis (1-(3, 5-dimethylphenyl)vinyl)-4-methylaniline

    [0264] ##STR00105##

    [0265] A 100 mL flask equipped with a stir bar was charged with p-methylaniline (10.7 g, 100 mmol, 1 eq.), KSF montmorillonite (10 g), and 3, 5-dimethylphenylacetylene (28.6 g, 220 mmol, 2.2 eq.). The heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the resultant was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a white solid (12.51 g, Yield=34%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 6.98 (s, 4H), 6.95 (s, 2H), 6.91 (s, 2H), 5.72 (d, J=1.6 Hz, 2H), 5.31 (d, J=1.6 Hz, 2H), 2.30 (s, 3H), 2.27 (s, 12H).

    Synthesis of the 2, 6-bis ((R)-1-(3, 5-dimethylphenyl) ethyl)-4-methylaniline

    [0266] ##STR00106##

    [0267] In a 100 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.2 mol %) and (Rc,Sp)-DuanPhos (0.24 mol %) were dissolved in 6 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of 2, 6-bis (1-(3, 5-dimethylphenyl) vinyl)-4-methylaniline (7.43 g, 20 mmol, 1.0 equiv) in a minimal amount of MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 80 bar H.sub.2 and the mixture was stirred at ambient temperature for 48 h. The reaction mixture was suction filtered, washed with methanol, and the solid was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a white solid (7.31 g, Yield=98.3%). .sup.1H NMR (600 MHz, CDCl.sub.3) : 7.06 (s, 2H), 6.80 (s, 2H), 6.76 (s, 4H), 3.95 (q, J=7.1 Hz, 2H), 2.39 (s, 3H), 2.23 (s, 12H), 1.57 (d, J=7.1 Hz, 6H). .sup.13C NMR (151 MHz, CDCl.sub.3) : 145.3, 138.3, 128.4, 126.7, 125.4, 40.4, 22.5, 21.5, 21.4.

    Synthesis of the (1E,2E)-N.SUP.1.,N.SUP.2.-bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diimine

    [0268] ##STR00107##

    [0269] A 50 mL flask equipped with a stir bar was charged with 2, 6-bis ((R)-1-(3, 5-dimethylphenyl) ethyl)-4-methylaniline (7.0 g, 18.84 mmol) and 40 mL EtOH and heated under reflux for 1 h. Drops of acetic acid (5 mol %) was then added and reflux was continued. A 40% solution of glyoxal (0.5 eq) in water was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated at 80 C. for further 12 h and then cooled to room temperature. The mixture was purified by column chromatography to provide the title compound as a yellow solid (6.2 g, Yield=86%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.81 (s, 2H), 6.96 (s, 4H), 6.82 (d, J=7.4 Hz, 12H), 4.03 (q, J=7.1 Hz, 4H), 2.32 (s, 6H), 2.26 (s, 24H), 1.51 (d, J=7.2 Hz, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) : 164.1, 146.3, 137.8, 134.4, 129.1, 121.8, 39.0, 22.0.

    Synthesis of the N.SUP.1.,N.SUP.2.-bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diamine

    [0270] ##STR00108##

    [0271] A 100 mL flask equipped with a stir bar was charged with (1E,2E)-N.sup.1,N.sup.2-bis(2,6-bis((R).sub.1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diimine (6.0 g, 7.83 mmol), 40 mL THF, and LiAlH.sub.4 (3.0 eq) under a nitrogen atmosphere. The mixture was stirred at room temperature for 12 h. Saturated KOH solution was added, and the mixture was extracted with EtOAc, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford the title compound (5.88 g, Yield=97.5%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.01 (s, 4H), 6.81 (s, 12H), 4.35 (q, J=7.2 Hz, 4H), 2.95-2.74 (m, 2H), 2.58-2.48 (m, 2H), 2.34 (s, 6H), 2.25 (s, 24H), 1.54 (d, J=7.1 Hz, 12H).

    Synthesis of the 1,3-bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0272] ##STR00109##

    [0273] A 50 mL flask equipped with a stir bar was charged with N.sup.1,N.sup.2-bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diamine (1.0 g, 770 mmol), NH.sub.4Cl (104 mg, 1.95 mmol, 1.5 eq.), and 10 mL HC(OEt).sub.3 under a nitrogen atmosphere. The mixture was stirred at 115 C. for 15 h and then cooled to room temperature. The crude product was was purified by column chromatography to afford the title saturated imidazolium salt as a white solid (693 mg, Yield=65.3%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 10.81 (s, 1H), 7.26 (s, 2H), 7.14 (s, 4H), 7.01 (s, 2H), 6.93 (s, 2H), 6.86 (s, 2H), 6.77 (s, 4H), 6.47 (s, 2H), 4.26 (q, J=7.1 Hz, 2H), 4.06 (q, J=6.9 Hz, 2H), 3.75-3.63 (m, 2H), 3.31-3.12 (m, 6H), 2.33 (d, J=9.7 Hz, 12H), 2.18 (s, 12H), 1.72 (d, J=7.1 Hz, 6H), 1.40 (d, J=6.9 Hz, 6H). .sup.13C NMR (101 MHz, CDCl.sub.3) : 161.6, 146.0, 144.2, 143.4, 142.1, 141.2, 138.6, 138.4, 128.8, 128.6, 128.5, 128.4, 127.9, 125.2, 124.8, 52.8, 40.2, 38.2, 23.2, 22.1, 21.8, 21.5, 21.4.

    Example 10

    Synthesis of the 1,3-bis(2,6-bis((R)-1-(3,5-di-tert-butylphenyl)ethyl)-4-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0274] ##STR00110## ##STR00111##

    Synthesis of the ((3, 5-di-tert-butylphenyl) ethynyl) trimethylsilane

    [0275] ##STR00112##

    [0276] A 300 mL flask equipped with a stir bar was charged with 3, 5-di-tert-butyl bromobenzene (53.8 g, 200 mmol), trimethylethynyl silicon (34 mL, 240 mmol), cuprous iodide (762 mg, 4 mmol %), bis (triphenylphosphine) palladium (II) chloride (1.4 g, 2 mmol) and 150 mL Et.sub.3N. The mixture was stirred at 100 C. for 24 h. The crude product was filtration, concentrated and used directly in the next step.

    Synthesis of the 1, 3-di-tert-butyl-5-ethynylbenzene

    [0277] ##STR00113##

    [0278] A 1 L flask equipped with a stir bar was charged with ((3, 5-di-tert-butylphenyl) ethynyl) trimethylsilane, 350 mL MeOH, K.sub.2CO.sub.3 (41.5 g, 300 mmol). The mixture was stirred at room temperature for 12 h. The MeOH solution was removed by concentrated, diluted with ether and washed with saturated NaCl solution, combined organic layer, and dried over Na.sub.2SO.sub.4. The crude product was purified by column chromatography to provide the title compound as a pale yellow liquid (38.6 g, Yield=90%).

    Synthesis of the 2, 6-bis (1-(3, 5-di-tert-butylphenyl) vinyl)-4-methylaniline

    [0279] ##STR00114##

    [0280] A 100 mL flask equipped with a stir bar was charged with p-methylaniline (10.7 g, 100 mmol, 1 eq.), KSF montmorillonite (10 g), and 1, 3-di-tert-butyl-5-ethynylbenzene (47.08 g, 220 mmol, 2.2 eq.). The heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the residue was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a yellow solid (19.9 g, Yield=37.2%).

    Synthesis of the 2, 6-bis ((R)-1-(3, 5-di-tert-butylphenyl) ethyl)-4-methylaniline

    [0281] ##STR00115##

    [0282] In a 100 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.3 mol %) and (Rc,Sp)-DuanPhos (0.36 mol %) were dissolved in 12 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of 2, 6-bis (1-(3, 5-di-tert-butylphenyl) vinyl)-4-methylaniline (18.5 g, 34.5 mmol) in 120 mL MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 80 bar H.sub.2 and the mixture was stirred at ambient temperature for 48 h. The solvent was removed under reduced pressure, and the residue was purified by column chromatography to provide the title compound as a liquid (13.0 g, Yield=70%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.22 (t, J=1.8 Hz, 2H), 7.02 (d, J=1.9 Hz, 4H), 6.97 (s, 2H), 4.02 (q, J=7.1 Hz, 2H), 3.29 (s, 2H), 2.33 (s, 3H), 1.59 (d, J=7.2 Hz, 6H), 1.25 (s, 36H).

    Synthesis of the N.SUP.1., N.SUP.2.-bis (2, 6-bis ((R)-1-(3, 5-di-tert-butylphenyl) ethyl)-4-methylphenyl) oxamide

    [0283] ##STR00116##

    [0284] A 50 mL flask equipped with a stir bar was charged with 2, 6-bis ((R)-1-(3, 5-di-tert-butylphenyl) ethyl)-4-methylaniline (1.89 g, 3.5 mol), Et.sub.3N (535 L, 3.9 mol), 15 mL THF and cooled to 0 C. Drops of oxalyl chloride (163 L, 1.9 mol) was added. The reaction mixture was stirred overnight. Saturated NaHCO.sub.3 solution was added, and the mixture was extracted with DCM, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford the title product (1.68 g, Yield=85%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.58 (s, 2H), 7.25-7.20 (m, 4H), 7.08 (d, J=1.8 Hz, 8H), 6.93 (s, 4H), 4.23 (q, J=7.0 Hz, 4H), 2.27 (s, 6H), 1.54 (d, J=7.1 Hz, 6H), 1.26 (s, 72H), 0.93 (d, J=6.6 Hz, 6H).

    Synthesis of the N.SUP.1., N.SUP.2.-bis (2,6-bis ((R)-1-(3,5-di-tert-butylphenyl) ethyl)-4-methylphenyl) ethane-1, 2-diamine

    [0285] ##STR00117##

    [0286] A 100 mL flask equipped with a stir bar was charged with N.sup.1, N.sup.2-bis (2, 6-bis ((R)-1-(3, 5-di-tert-butylphenyl) ethyl)-4-methylphenyl) ethane-1, 2-diamine (3.0 g, 2.65 mmol), 30 mL THF, and LiAlH.sub.4 (3.0 eq) under a nitrogen atmosphere. The mixture was stirred for 24 h. Saturated KOH solution was added, and the mixture was extracted with EtOAc, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford the title compound (1.8 g, Yield=62%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.22 (t, J=1.8 Hz, 4H), 7.12 (d, J=1.9 Hz, 8H), 7.01 (s, 4H), 4.62 (q, J=7.1 Hz, 4H), 3.12 (d, 0.1=7.2 Hz, 2H), 2.60 (d, 0.1=7.5 Hz, 2H), 2.35 (s, 6H), 1.65 (d, J=7.1 Hz, 12H), 1.25 (s, 72H).

    Synthesis of the 1,3-bis(2,6-bis((R)-1-(3,5-di-tert-butylphenyl)ethyl)-4-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0287] ##STR00118##

    [0288] A 10 mL flask equipped with a stir bar was charged with N.sup.1,N.sup.2-bis(2,6-bis((R)-1-(3,5-dimethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diamine (829 mg, 0.75 mmol), NRIC1 (48.1 mg, 0.9 mmo) and 4 mL HC(OEt).sub.3 under a nitrogen atmosphere. The mixture was stirred at 115 C. for 15 h and then cooled to room temperature. The crude product was was purified by column chromatography to afford the title saturated imidazolium salt (778 mg, Yield=90%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.24 (s, 1H), 7.29 (d, J=2.2 Hz, 4H), 7.04 (s, 4H), 6.92 (t, J=1.9 Hz, 8H), 4.49-4.32 (m, 4H), 4.20 (d, J=11.4 Hz, 2H), 3.89 (q, J=7.0 Hz, 2H), 2.31 (s, 6H), 1.84 (d, J=7.0 Hz, 6H), 1.30 (s, 36H), 1.19 (s, 36H), 1.06 (d, J=7.1 Hz, 6H).

    Example 11

    [0289] ##STR00119##

    Synthesis of the 5-bromo-1, 3-di-tert-butyl-2-methoxybenzene

    [0290] ##STR00120##

    [0291] A 500 mL flask equipped with a stir bar was charged with 200 mL THF, NaH (3.2 g, 131.5 mmol), 4-bromo-2, 6-di-tert-butylphenol (25 g, 87.7 mmol) and THF. The mixture was stirred at room temperature for 1 h. After dimethyl sulfate (9.1 mL, 96.4 mmol) was added dropwise, the mixture was heated to 75 C. for 12 h and then cooled to room temperature. 100 mL H.sub.2O was added, and the mixture was extracted with EtOAc, combined organic layer, and dried over Na.sub.2SO.sub.4. The crude product obtained after filtration and concentration in vacuo was purified by column chromatography to afford the title compound (23.4 g, Yield=89%). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.33 (s, 2H), 3.67 (s, 3H), 1.40 (s, 18H).

    Synthesis of the ((3, 5-Di-tert-butyl-4-methoxyphenyl) ethynyl) trimethylsilane

    [0292] ##STR00121##

    [0293] A 300 mL flask equipped with a stir bar was charged with 5-bromo-1,3-di-tert-butyl-2-methoxybenzene (26 g, 87 mmol), trimethylethynyl silicon (14.1 mL, 100 mmol), cuprous iodide (332 mg, 1.74 mmol), bis (triphenylphosphine) palladium (II) chloride (611 mg, 0.87 mmol) and 60 mL Et.sub.3N. The mixture was stirred at 75 C. for 12 h. The crude product was filtration, concentrated and used directly in the next step.

    [0294] A 1 L round-bottom flask equipped with a stir bar was charged with ((3, 5-Di-tert-butyl-4-methoxyphenyl) ethynyl) trimethylsilane, 120 mL MeOH, K.sub.2CO.sub.3 (30 g, 218 mol). The mixture was stirred at room temperature for 9 h. The MeOH solution was removed by concentrated, diluted with ether. The mixture was washed with water, combined organic layer and dried over Na.sub.2SO.sub.4. The crude product was purified by column chromatography to provide the title compound as a colorless liquid (19.1 g, Yield=90%). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.35 (s, 2H), 3.65 (s, 3H), 1.41 (s, 18H), 0.25 (s, 9H).

    Synthesis of the 2, 6-bis (1-(3, 5-di-tert-butyl-4-methoxyphenyl) vinyl)-4-methylaniline

    [0295] ##STR00122##

    [0296] A 350 mL flask equipped with a stir bar was charged with p-methylaniline (7.3 g, 68 mmol, 1 eq.), KSF montmorillonite (5 g), and 1, 3-di-tert-butyl-5-ethynyl-2-methoxybenzene (36.6 g, 150 mmol, 2.2 eq.). The heterogeneous slurry was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the resultant was purified by column chromatography to provide the title compound as a yellow solid (13.4 g, Yield=33%). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.28 (s, 4H), 6.88 (d, J=0.8 Hz, 2H), 5.71 (d, J=1.6 Hz, 2H), 5.27 (d, J=1.6 Hz, 2H), 3.65 (s, 6H), 2.25 (s, 3H), 1.37 (s, 26H).

    Synthesis of the 2, 6-bis ((R)-1-(3, 5-di-tert-butylphenyl-4-methoxyphenyl) ethyl)-4-methylaniline

    [0297] ##STR00123##

    [0298] In a 300 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.25 mol %) and (Rc,Sp)-DuanPhos (0.3 mol %) were dissolved in 12 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of 2, 6-bis (1-(3, 5-di-tert-butyl-4-methoxyphenyl) vinyl)-4-methylaniline (13.4 g, 22.4 mmol) in 120 mL MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 50 bar H.sub.2 and the mixture was stirred at ambient temperature for 48 h. The solvent was removed under reduced pressure, and the residue was purified by column chromatography to provide the title compound as a yellow solid (12.1 g, Yield=90%). .sup.1H NMR (400 MHz, CDCl.sub.3) 7.03 (s, 4H), 6.92 (s, 2H), 3.97 (q, J=7.1 Hz, 2H), 3.64 (s, 6H), 2.31 (s, 3H), 1.56 (d, J=7.1 Hz, 6H), 1.34 (s, 36H).

    Synthesis of the (1E,2E)-N.SUP.1.,N.SUP.2.-bis(2,6-bis((R)-1-(3,5-di-tert-butyl-4-methoxyphenyl)ethyl)-4-methylphenyl)acenaphthylene-1,2-diimine

    [0299] ##STR00124##

    [0300] A 100 mL flask equipped with a stir bar was charged with 2, 6-bis ((R)-1-(3, 5-di-tert-butylphenyl-4-methoxyphenyl) ethyl)-4-methylaniline (2.1 g, 3.5 mmol), quinone (318 mg, 1.75 mmol), p-toluenesulfonic acid monohydrate (67 mg, 0.35 mmol) and 35 mL toluene. The mixture was refluxed with vigorous stirring at 140 C. for 14 h. The reaction vessel was allowed to cool to room temperature before suction filtration, and the crude diimine was used directly in the next step.

    Synthesis of the 7,9-bis(2,6-bis((R)-1-(3,5-di-tert-butyl-4-methoxyphenyl)ethyl)-4-methylphenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium chloride

    [0301] ##STR00125##

    [0302] A 100 mL flask equipped with a stir bar was charged with the crude diimine, chloromethyl ether (1.5 g, 16 mmol). The mixture was refluxed with vigorous stirring at 80 C. for 24 h. The residue was purified by column chromatography to provide the title compound (312 mg, Yield=43%). .sup.1H NMR (400 MHz, CDCl.sub.3) 8.66 (s, 1H), 8.00 (d, J=8.3 Hz, 2H), 7.45 (dd, J=8.3, 7.1 Hz, 2H), 7.40 (d, J=1.8 Hz, 2H), 7.28 (s, 1H), 7.26 (s, 2H), 6.89 (d, J=7.0 Hz, 2H), 6.85 (s, 4H), 6.54 (s, 4H), 4.00 (q, J=7.0 Hz, 2H), 3.66 (s, 8H), 3.47 (s, 8H), 3.44 (s, 6H), 3.23 (q, J=7.0 Hz, 2H), 2.54 (s, 6H), 1.59 (d, J=7.1 Hz, 6H), 1.07 (d, J=7.1 Hz, 6H), 1.00 (s, 36H).

    Example 12

    Synthesis of the 1,3-bis(2,6-bis((R)-1-(3,5-diethylphenyl)ethyl)-4-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0303] ##STR00126## ##STR00127##

    Synthesis of the ((3, 5-diethylphenyl) ethynyl) trimethylsilane

    [0304] ##STR00128##

    [0305] A 300 mL flask equipped with a stir bar was charged with 3, 5-diethylbromobenzene (53.1 g, 249 mmol), trimethylethynyl silicon (31.1 g, 323.7 mmol), cuprous iodide (1.9 g, 4 mmol %), bis (triphenylphosphine) palladium (II) chloride (3.5 g, 2 mmol) and 250 mL Et.sub.3N. The mixture was stirred at 100 C. for 24 h and then cooled to room temperature. The crude product was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a pale yellow liquid (54.6 g, Yield=95.3%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.16 (s, 2H), 6.99 (s, 1H), 2.60 (q, J=7.6 Hz, 4H), 1.23 (t, J=7.6 Hz, 6H), 0.26 (s, 9H).

    Synthesis of the 1, 3-diethyl-5-ethynylbenzene

    [0306] ##STR00129##

    [0307] A 1 L flask equipped with a stir bar was charged with ((3, 5-diethylphenyl) ethynyl) trimethylsilane (57.27 g, 249 mmol, 1.0 equiv), 300 mL MeOH, K.sub.2CO.sub.3 (103.2 g, 747 mmol). The mixture was stirred at room temperature for 12 h. The MeOH solution was removed by concentrated, diluted with ether and the mixture was washed with brine, combined organic layer, and dried over Na.sub.2SO.sub.4. The crude product was purified by column chromatography to provide the title compound as a pale yellow liquid (36.5 g, Yield=94%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.19 (s, 2H), 7.04 (s, 1H), 3.04 (s, 1H), 2.62 (q, J=7.6 Hz, 4H), 1.24 (t, J=7.6 Hz, 6H).

    Synthesis of the 2, 6-bis (1-(3, 5-diethylphenyl) vinyl)-4-methylaniline

    [0308] ##STR00130##

    [0309] A 100 mL flask equipped with a stir bar was charged with p-methylaniline (10.7 g, 100 mmol, 1 eq.), KSF montmorillonite (10 g), and 1, 3-diethyl-5-ethynylbenzene (34.8 g, 220 mmol, 2.2 eq.). The reaction mixture was refluxed with vigorous stirring at 140 C. for 8 h. The reaction vessel was allowed to cool to room temperature before dilution with ethyl acetate and filtration. The solvent was removed from the mother liquor under reduced pressure, and the resultant was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a white solid (13.05 g, Yield=30.8%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.02 (d, J=1.7 Hz, 4H), 6.95 (d, J=1.0 Hz, 4H), 5.74 (d, J=1.7 Hz, 2H), 5.32 (d, J=1.7 Hz, 2H), 3.39 (s, 2H), 2.58 (q, J=7.6 Hz, 8H), 2.29 (s, 3H), 1.19 (t, J=7.6 Hz, 12H).

    Synthesis of the 2, 6-bis ((R)-1-(3, 5-diethylphenyl)ethyl)-4-methylaniline

    [0310] ##STR00131##

    [0311] In a 100 mL microwave tube, (NBD).sub.2RhBF.sub.4 (0.2 mol %) and (Rc,Sp)-DuanPhos (0.24 mol %) were dissolved in 6 mL DCM under a nitrogen atmosphere and stirred for 15 min. A solution of 2, 6-bis (1-(3, 5-diethylphenyl) vinyl)-4-methylaniline (7.3 g, 17.26 mmol, 1.0 equiv) in 60 mL MeOH was added. The microwave tube was transferred into the autoclave and the reactor was purged three times with H.sub.2. The reactor was pressurized to 80 bar H.sub.2 and the mixture was stirred at ambient temperature for 48 h. The solvent was removed under reduced pressure, and the residue was purified by column chromatography (0-2% EtOAc in hexanes) to provide the title compound as a yellow solid (7.1 g, Yield=96.3%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.04 (s, 2H), 6.85 (d, J=1.6 Hz, 2H), 6.81 (d, J=1.5 Hz, 4H), 3.95 (q, J=7.1 Hz, 2H), 3.28 (s, 2H), 2.55 (q, 0.1=7.6 Hz, 8H), 2.39 (s, 3H), 1.58 (d, 0.1=7.2 Hz, 6H), 1.18 (t, 0.1=7.6 Hz, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) : 146.0, 144.6, 140.0, 130.3, 126.6, 126.3, 125.5, 124.4, 40.8, 28.9, 22.4, 21.4, 15.7.

    Synthesis of the (1E,2E)-N.SUP.1.,N.SUP.2.-bis(2,6-bis((R)-1-(3,5-diethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diimine

    [0312] ##STR00132##

    [0313] A 50 mL flask equipped with a stir bar was charged with 2, 6-bis ((R)-1-(3, 5-diethylphenyl) ethyl)-4-methylaniline (2.7 g, 6.23 mol) and 40 mL EtOH and was heated under reflux for 1 h. Drops of acetic acid (5 mol %) was then added. A 40% solution of glyoxal (0.5 eq) in water was added with the aid of a dropping funnel over a period of 30 min, and the resulting mixture was heated at 80 C. for further 12 h and then cooled to room temperature. The mixture was purified by column chromatography to provide the title compound as a yellow solid (2.23 g, Yield=81%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.85 (s, 2H), 7.04 (s, 2H), 6.92 (s, 4H), 6.89-6.83 (m, 8H), 6.80 (d, 0.1=1.6 Hz, 2H), 4.06 (t, 0.1=6.9 Hz, 2H), 3.95 (q, 0.1=7.2 Hz, 2H), 2.55 (m, 16H), 2.28 (s, 6H), 1.58 (d, J=6.9 Hz, 6H), 1.49 (d, J=7.2 Hz, 6H), 1.22-1.13 (m, 24H).

    Synthesis of the N.SUP.1., N.SUP.2.-bis (2, 6-bis ((R)-1-(3, 5-diethylphenyl) ethyl)-4-methylphenyl) ethane-1, 2-diamine

    [0314] ##STR00133##

    [0315] A 100 mL flask equipped with a stir bar was charged with (1E,2E)-N.sup.1,N.sup.2-bis(2,6-bis((R)-1-(3,5-diethylphenyl)ethyl)-4-methylphenyl)ethane-1,2-diimine (2.2 g, 2.51 mmol), 40 mL THF, and LiAlH.sub.4 (3.0 eq) under a nitrogen atmosphere. The mixture was stirred for 12 h. Saturated KOH solution was added, and the mixture was extracted with EtOAc, combined organic layer and dried over Na.sub.2SO.sub.4. After filtration and concentration in vacuo, the residue was purified by column chromatography to afford the title compound (2.05 g, Yield=93%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 6.90 (d, J=4.8 Hz, 4H), 6.81 (m, 12H), 4.42 (q, J=7.2 Hz, 4H), 2.88 (d, J=7.2 Hz, 2H), 2.59 (d, J=7.3 Hz, 2H), 2.49 (q, J=7.6 Hz, 16H), 2.26 (s, 6H), 1.54 (d, J=7.2 Hz, 12H), 1.12 (t, J=7.6 Hz, 24H).

    Synthesis of the 1,3-bis(2,6-bis((R)-1-(3,5-diethylphenyl)ethyl)-4-methylphenyl)-4,5-dihydro-1H-imidazol-3-ium chloride

    [0316] ##STR00134##

    [0317] A 50 mL flask equipped with a stir bar was charged with N.sup.1, N.sup.2-bis (2, 6-bis ((R)-1-(3, 5-diethylphenyl) ethyl)-4-methylphenyl) ethane-1, 2-diamine (1.22 g, 1.38 mmol), NH.sub.4Cl (111 mg, 2.07 mmol, 1.5 eq.) and 10 mL HC(OEt).sub.3 under a nitrogen atmosphere. The mixture was stirred at 115 C. for 15 h and then cooled to room temperature. The crude product was was purified by column chromatography to afford the title compound as a white solid (866 mg, Yield=67.6%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 10.41 (s, 1H), 7.13 (m, 4H), 7.00-6.80 (m, 12H), 4.25 (q, J=7.0 Hz, 2H), 4.01 (q, J=6.8 Hz, 2H), 3.69-3.60 (m, 2H), 3.22-3.13 (m, 2H), 2.66-2.57 (m, 16H), 2.34 (s, 6H), 1.72 (d, J=7.0 Hz 6H), 1.37 (d, J=7.0 Hz, 6H), 1.21-1.14 (m, 24H).

    Example 13

    Synthesis of the 7,9-bis(2,6-bis((R)-1-(3,5-diethylphenyl)ethyl)-4-methylphenyl)-7H-acenaphtho[1,2-d]imidazol-9-ium chloride

    [0318] ##STR00135##

    [0319] A 100 mL flask equipped with a stir bar was charged with 2, 6-bis ((R)-1-(3, 5-diethylphenyl) ethyl)-4-methylaniline (3 g, 7.0 mmol), quinone (609 mg, 3.3 mmol), p-toluenesulfonic acid monohydrate (251 mg, 1.32 mmol) and 30 mL toluene. The mixture was refluxed with vigorous stirring at 140 C. for 14 h. The reaction vessel was cooled to room temperature before suction filtration, and the crude diimine was used directly in the next step. A 100 mL flask equipped with a stir bar was charged with the crude diimine compound, chloromethyl ether (20 g, 210 mmol). The mixture was refluxed with vigorous stirring at 80 C. for 24 h. The residue was purified by column chromatography to provide the title compound (3.01 g, Yield=41%). .sup.1H NMR (400 MHz, CDCl.sub.3) : 10.08 (s, 1H), 7.80 (d, J=8.3 Hz, 2H), 7.43 (d, J=1.8 Hz, 2H), 7.25-7.09 (m, 6H), 6.90 (m, 8H), 6.60 (d, J=7.0 Hz, 2H), 6.17 (m, 2H), 4.06 (q, J=7.0 Hz, 4H), 2.59 (q, J=7.4 Hz, 16H), 2.53 (s, 6H), 1.59 (d, J=7.1 Hz, 12H), 1.14 (t, J=7.6 Hz, 24H).

    APPLICATION EXAMPLES

    [0320] In the following application examples, branched/linear ratio (rr) was determined by .sup.1H NMR, GC, and GC-MS analysis.

    Application Examples 1

    [0321] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor 7:

    ##STR00136##

    [0322] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), carbene precursor 7 (3.1 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0323] The crude product (75:25 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 61% yield. .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.27 (t, J=7.1 Hz, 2H), 7.22-7.17 (m, 3H), 2.65-2.56 (m, 2H), 1.79-1.71 (m, 3H), 1.58-1.49 (m, 1H), 1.34-1.28 (m, 12H), 0.97 (d, J=6.4 Hz, 3H), 0.93-0.90 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 143.77, 128.46, 128.13, 125.32, 69.99, 48.86, 35.81, 35.60, 31.83, 15.93. [].sub.D.sup.20=+5.2 (c=0.25, CHCl3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=80%: tR (minor)=9.3 min, tR (major)=12.6 min. HRMS (ESI) calculated for C.sub.17H.sub.28BO.sub.2 [M+H].sup.+ m/z 274.2213, found 274.2213.

    Application Examples 2

    [0324] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor 16:

    ##STR00137##

    [0325] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), carbene precursor 16 (2.9 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0326] The crude product (79:21 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 54% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=84%: tR (minor)=9.3 min, tR (major)=12.6 min.

    [0327] Application Examples 3

    [0328] Catalytic asymmetric hydroboration reactions by using Cu/NHC complex 17:

    ##STR00138##

    [0329] In a nitrogen-filled glove box, compound 17 (3.1 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0330] The crude product (75:25 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 6.sub.5% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=80%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 4

    [0331] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor:

    ##STR00139##

    [0332] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), 1,3-bis (2,6-bis ((R)-1-(3-methylphenyl) ethyl)-2-methylphenyl)-4,5-dihydro-1H-imidazole chloride (3.2 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0333] The crude product (82:18 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 76% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=96%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 5

    [0334] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor:

    ##STR00140##

    [0335] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), 1,3-bis (2,6-bis ((R)-1-(3,5-dimethylphenyl) ethyl)-2-methylphenyl)-4,5-dihydro-1H-imidazole chloride (3.2 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0336] The crude product (86:14 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 79% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=97%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 6

    [0337] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor:

    ##STR00141##

    [0338] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), 1,3-bis (2,6-bis ((R)-1-(3,5-di-tert-butylphenyl) ethyl)-2-methylphenyl)-4,5-dihydro-1H-imidazole chloride (3.6 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0339] The crude product (90:10 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 80% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=97%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 7

    [0340] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor:

    ##STR00142##

    [0341] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), 7,9-bis (2,6-bis ((R)-1-(3,5-di-tert-butyl-4-methoxyphenyl) ethyl)-4-methylphenyl)-7H-Pyre [1,2-d] imidazole chloride (4.2 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0342] The crude product (90:10 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 80% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=97%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 8

    [0343] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor:

    ##STR00143##

    [0344] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), 1,3-bis (2,6-bis ((R)-1-(3,5-diethylphenyl) ethyl)-2-methylphenyl)-4,5-dihydro-1H-imidazole chloride (3.6 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0345] The crude product (88:12 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 78% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=96%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 9

    [0346] Catalytic Asymmetric Hydroboration Reactions by Using Carbene Precursor:

    ##STR00144##

    [0347] In a nitrogen-filled glove box, CuCl (0.4 mg, 0.004 mmol, 2.0 mol %), 7,9-bis (2,6-bis ((R)-1-(3,5-diethylphenyl) ethyl)-4-methylphenyl)-7H-pyrene [1,2-d] imidazole chloride (4.1 mg, 0.004 mmol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The unactivated terminal alkene S1 (26.4 mg, 0.2 mmol) and MeOH (16 uL, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography (PE:EA=40:1) to afford the desired product 37a. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH) of the isolated products unless otherwise stated.

    [0348] The crude product (88:12 rr) was purified by column chromatography to provide the title compound as a colorless liquid in 80% yield. HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=97%: t.sub.R (minor)=9.3 min, t.sub.R (major)=12.6 min.

    Application Examples 10

    Synthesis of the (R,R,R,R)-ANIPE-CuCl (compound 35)

    [0349] ##STR00145##

    [0350] CuCl (100 mg, 1.0 mmol, 1.0 equiv), tBuOK (112 mg, 1.0 mmol, 1.0 equiv), (R,R,R,R)-ANIPE/HCl compound 25 (824 mg, 1.0 mmol, 1.0 equiv) and THF (5 mL) were added to a flame-dried Schlenk tube. The mixture was stirred at rt for 12 h. The reaction mixture was filtered through a short pad of Celite, and the solvent was removed in vacuo. The crude product was purified by flash column chromatography (DCM) to provide the title compound as a yellow powder in 90% yield (779 mg). Melting point: 159-160 C. IR: 2967, 2920, 1603, 1490, 1446, 1064, 756, 700; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.70 (d, J=8.2 Hz, 2H), 7.41 (d, J=7.5 Hz, 4H), 7.33 (t, 0.1=7.4 Hz, 4H), 7.27 (t, 0.1=7.7 Hz, 2H), 7.22-7.15 (m, 4H), 7.03 (s, 2H), 6.83-6.70 (m, 12H), 4.24 (q, J=6.3 Hz, 2H), 3.96 (q, J=6.5 Hz, 2H), 2.40 (s, 6H), 1.49 (dd, J=13.3, 7.0 Hz, 12H). .sup.13C NMR (101 MHz, CDCl.sub.3) : 186.13, 144.85, 143.92, 143.60, 143.20, 140.58, 139.05, 131.99, 130.38, 129.26, 128.77, 128.00, 127.91, 127.77, 127.48, 127.31, 127.14, 126.41, 125.81, 124.85, 121.43, 39.78, 38.39, 22.64, 21.88, 21.62. [].sub.D.sup.20=+251.2 (c=0.90, CHCl.sub.3). HRMS (ESI) calculated for C.sub.59H.sub.52N.sub.2ClCu [M].sup.+ m/z 886.3110, found 886.3105.

    Synthesis of the Single Crystal of (R,R,R,R)-ANIPE-CuCl (Compound 35)

    [0351] (R,R,R,R)-ANIPE-CuCl (10 mg) was dissolved in 2 ml ether and sonicated for 1 min. Filtered with cotton into an 8 ml vial. After sealing the membrane tightly, pierce 3 to 5 small holes with a capillary. The vial was carefully placed in a wide-mouth bottle containing n-pentane. After standing for one week, the square crystals were taken out under a microscope and tested for single crystals. FIG. 1 shows the single-crystal diffraction pattern of compound 35.

    Example 11

    [0352] Catalytic Asymmetric Markovnikov Hydroboration of -Olefins

    ##STR00146##

    [0353] In a nitrogen-filled glove box, (R,R,R,R)-ANIPE-CuCl (3.4 mg, 4 mol, 2.0 mol %), tBuONa (28.8 mg, 0.3 mmol, 1.5 equiv) and n-hexane (1.0 mL) were charged to a 8 ml vial equipped with a magnetic stirrer bar. The reaction mixture was allowed to stir at rt for 1 h, followed by addition of B.sub.2dmpd.sub.2 (113 mg, 0.4 mmol, 2.0 equiv). Stirring was continued for an additional 0.5 h at rt. The alkene (0.2 mmol) and MeOH (16 L, 0.4 mmol, 2.0 equiv) were then added. The reaction vial was removed from the glove box, and the reaction mixture was stirred within the sealed vial at rt for 24 h. The resulting mixture was then filtered through a short pad of silica gel, eluting with EtOAc. The branched/linear ratio (rr) was determined by GC-MS analysis at this stage. The solvent was removed in vacuo, and the crude residue was purified via column chromatography to afford the desired product. Enantiomeric excess (ee) values were determined by either chiral HPLC or SFC analysis following oxidation (H.sub.2O.sub.2/NaOH or NaBO.sub.3) of the isolated products unless otherwise stated.

    [0354] Compound 37a

    ##STR00147##

    [0355] The regioselectivity of the crude product is (Markov:anti-Markov) 80:20, anhydrous oil, yield=67%, .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.27 (t, J=7.1 Hz, 2H), 7.22-7.17 (m, 3H), 2.65-2.56 (m, 2H), 1.79-1.71 (m, 3H), 1.58-1.49 (m, 1H), 1.34-1.28 (m, 12H), 0.97 (d, J=6.4 Hz, 3H), 0.93-0.90 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 143.77, 128.46, 128.13, 125.32, 69.99, 48.86, 35.81, 35.60, 31.83, 15.93. [].sub.D.sup.20=+5.2 (c=0.25, CHCl.sub.3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm), ee=96%: t.sub.R(minor)=9.3 min, t.sub.R (major)=12.6 min. HRMS (ESI) calculated for C.sub.17H.sub.28BO.sub.2 [M+H].sup.+ 274.2213, found 274.2213.

    [0356] Compound 37b

    ##STR00148##

    [0357] The regioselectivity of the crude product is (Markov:anti-Markov) 81:19, yellow oil, yield=50%, .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.58 (d, J=8.0 Hz, 2H), 7.44 (d, J=8.0 Hz, 2H), 4.54 (s, 2H), 3.47 (t, J=6.6 Hz, 2H), 1.75 (s, 2H), 1.67-1.54 (m, 2H), 1.46-1.33 (m, 4H), 1.29 (s, 12H), 1.26-1.16 (m, 2H), 0.88 (d, J=7.0 Hz, 3H), 0.84-0.74 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 142.91, 127.42, 125.24, 125.20, 71.98, 71.02, 69.85, 48.85, 33.39, 31.75, 29.72, 28.81, 26.43, 15.91. [].sub.D.sup.20=+3.8 (c=0.4, CHCl.sub.3). HPLC (IA, 2% IPA in hexanes, 0.8 mL/min, 220 nm) ee=92%: t.sub.R (major)=21.2 min, t.sub.R (minor)=22.2 min. HRMS (ESI) calculated for C.sub.22H.sub.38BO.sub.3NF.sub.3 [M+NH.sub.4].sup.+ 431.2928, found 431.2922.

    [0358] Compound 37c

    ##STR00149##

    [0359] The regioselectivity of the crude product is (Markov:anti-Markov) 86:14, yellow oil, yield=67%. .sup.1H NMR (400 MHz, CDCl.sub.3) : 6.84 (s, 1H), 6.78-6.77 (m, 2H), 5.93 (s, 2H), 4.38 (s, 2H), 3.41 (t, J=6.7 Hz, 2H), 1.75 (s, 2H), 1.63-1.53 (m, 2H), 1.45-1.30 (m, 4H), 1.29 (s, 12H), 1.26-1.13 (m, 2H), 0.87 (d, J=7.0 Hz, 3H), 0.83-0.72 (in, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 147.66, 146.91, 132.64, 121.11, 108.39, 107.97, 104.99, 100.87, 72.69, 70.42, 69.84, 48.86, 33.41, 31.77, 29.76, 28.85, 26.47, 15.92. [].sub.D.sup.20=+4.5 (c=0.24, CHCl.sub.3). HPLC (IA, 2% IPA in hexanes, 0.8 mL/min, 220 nm) ee=91%: t.sub.R (major)=44.2 min, t.sub.R (minor)=46.3 min. HRMS (ESI)calculated for C.sub.22H.sub.39BNO.sub.5[M+NH.sub.4] 407.2952, found 407.2948.

    [0360] Compound 37d

    ##STR00150##

    [0361] The regioselectivity of the crude product is (Markov:anti-Markov) 84:16, colorless oil, yield=61%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.35 (d, J=8.4 Hz, 2H), 7.17 (d, J=8.1 Hz, 2H), 4.47 (s, 2H), 3.46 (t, J=6.7 Hz, 2H), 1.75 (s, 2H), 1.65-1.58 (m, 2H), 1.46-1.33 (m, 4H), 1.29 (s, 12H), 1.26-1.15 (m, 2H), 0.88 (d, J=6.9 Hz, 3H), 0.84-0.72 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 148.48, 137.54, 128.81, 120.84, 71.91, 70.89, 69.84, 48.85, 33.39, 31.75, 29.73, 28.82, 26.44, 15.90. [].sub.D.sup.20=+3.6 (c=0.34, CHCl.sub.3). HPLC (IA, 2% IPA in hexanes, 0.8 mL/min, 220 nm) ee=90%: t.sub.R (major)=18.4 min, t.sub.R(minor)=19.2 min. HRMS (ESI) calculated for C.sub.22H.sub.38BF.sub.3NO.sub.4 [M+NH.sub.4].sup.+447.2877, found 447.2877.

    [0362] Compound 37e

    ##STR00151##

    [0363] The regioselectivity of the crude product is (Markov:anti-Markov) 83:17, colorless oil, yield=74%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.31 (d, J=6.8 Hz, 1H), 7.79 (d, J=8.4 Hz, 1H), 7.51-7.44 (m, 2H), 7.43-7.32 (m, 2H), 6.80 (d, 0.1=7.3 Hz, 1H), 4.13 (t, 0.1=6.4 Hz, 2H), 1.98-1.89 (m, 2H), 1.76 (s, 2H), 1.60-1.50 (m, 2H), 1.52-1.33 (m, 4H), 1.30 (s, 12H), 0.93 (d, J=6.8 Hz, 3H), 0.90-0.85 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 154.94, 134.48, 127.35, 126.25, 125.89, 125.78, 124.98, 122.15, 119.83, 104.49, 69.89, 68.19, 48.87, 33.45, 31.79, 29.34, 28.83, 26.55, 15.98. [].sub.D.sup.20=+5.1 (c=0.11, CHCl.sub.3). SFC (OD, 10% IPA in CO.sub.2, 1.3 mL/min, 214 nm) ee=95%: t.sub.R (major)=30.9 min, t.sub.R (minor)=32.3 min. HRMS (ESI) calculated for C.sub.24H.sub.39BNO.sub.3 [M+NH.sub.4].sup.+399.3054, found 399.3053.

    [0364] Compound 37f:

    ##STR00152##

    [0365] The regioselectivity of the crude product is (Markov:anti-Markov) 85:15, yellow oil, yield=63%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.24 (s, 4H), 4.44 (s, 2H), 3.43 (t, J=6.7 Hz, 2H), 2.47 (s, 3H), 1.75 (s, 2H), 1.66-1.53 (m, 2H), 1.46-1.31 (m, 3H), 1.29 (s, 12H), 1.26-1.11 (m, 3H), 0.87 (d, J=7.1 Hz, 3H), 0.83-0.72 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 137.38, 135.73, 128.21, 126.74, 72.38, 70.59, 69.85, 48.86, 33.41, 31.78, 29.77, 28.85, 26.47, 16.05, 15.92. [].sub.D.sup.20=+4.2 (c=0.27, CHCl.sub.3). HPLC (IA, 2% IPA in hexanes, 0.8 mL/min, 220 nm) ee=90%: t.sub.R (major)=41.5 min, t.sub.R (minor)=43.1 min. HRMS (ESI) calculated for C.sub.22H.sub.41O.sub.3BNS [M+NH.sub.4].sup.+409.2923, found 409.2931.

    [0366] Compound 37g

    ##STR00153##

    [0367] The regioselectivity of the crude product is (Markov:anti-Markov) 86:14, yellow oil, yield=53%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.26 (d, 0.1=4.9 Hz, 1H), 6.96 (d, 0.1=7.5 Hz, 2H), 4.64 (s, 2H), 3.46 (t, 0.1=6.7 Hz, 2H), 1.75 (s, 2H), 1.60-1.55 (m, 2H), 1.46-1.30 (m, 4H), 1.29 (s, 12H), 1.26-1.14 (m, 2H), 0.87 (d, J=7.2 Hz, 3H), 0.83-0.74 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 141.57, 126.52, 126.02, 125.50, 70.36, 69.84, 67.27, 48.86, 33.41, 31.78, 29.68, 28.84, 26.41, 15.92. [].sub.D.sup.20=+5.3 (c=0.41, CHCl.sub.3). HPLC (AS-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=95%: t.sub.R (major)=6.8 min, t.sub.R (minor)=10.1 min. HRMS (ESI) calculated for C.sub.19H.sub.37BNO.sub.3S[M+NH.sub.4].sup.+369.2618, found 369.2615.

    [0368] Compound 37h

    ##STR00154##

    [0369] The regioselectivity of the crude product is (Markov:anti-Markov) 83:17, anhydrous oil, yield=53%; .sup.1H NMR (400 MHz, CDCl.sub.3) : .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.38 (d, J=0.9 Hz, 1H), 6.31 (d, J=1.8 Hz, 1H), 6.28 (d, J=3.0 Hz, 1H), 4.42 (s, 2H), 3.44 (t, J=6.8 Hz, 2H), 1.75 (s, 2H), 1.62-1.54 (m, 3H), 1.38 m, 2H), 1.28 (s, 12H), 1.26-1.11 (m, 3H), 0.86 (d, J=7.0 Hz, 3H), 0.80-0.77 m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 152.15, 142.56, 110.14, 108.85, 104.99, 100.24, 70.58, 69.84, 64.69, 48.85, 33.39, 31.77, 29.62, 28.81, 26.36, 15.90. [].sub.D.sup.20=+4.9 (c=0.25, CHCl.sub.3). HPLC (AS-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=92%: t.sub.R (major)=7.2 min, t.sub.R (minor)=11.9 min. HRMS (ESI) calculated for C.sub.19H.sub.37O.sub.4BN [M+NH.sub.4].sup.+ 353.2846, found 353.2844.

    [0370] Compound 37i

    ##STR00155##

    [0371] The regioselectivity of the crude product is (Markov:anti-Markov) 85:15, anhydrous oil, yield=50%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.48 (t, J=2.7 Hz, 1H), 7.33-7.22 (m, 1H), 6.77 (d, J=8.8 Hz, 1H), 3.98 (t, 0.1=6.6 Hz, 2H), 1.87-1.77 (m, 2H), 1.76 (s, 2H), 1.51-1.39 (m, 4H), 1.29 (s, 12H), 1.27-1.17 (m, 2H), 0.89 (d, J=6.9 Hz, 3H), 0.85-0.77 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 153.97, 132.54, 130.35, 123.99, 114.42, 112.09, 69.88, 69.44, 48.83, 33.30, 31.77, 28.96, 28.64, 26.11, 15.92. [].sub.D.sup.20=+4.4 (c=0.36, CHCl.sub.3). HPLC analysis (AS-H, 1% IPA in hexanes, 1 mL/min, 254 nm) indicated 92% ee: t.sub.R (major)=13.7 min, t.sub.R (minor)=15.6 min. HRMS (EI) calculated for C.sub.20H.sub.31O.sub.3BClBr [M].sup.+ m/z 443.1274, found 443.1283.

    [0372] Compound 37j

    ##STR00156##

    [0373] The regioselectivity of the crude product is (Markov:anti-Markov) 82:18, anhydrous oil, yield=55%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.51 (d, 0.1=7.6 Hz, 2H), 6.64 (d, 0.1=7.7 Hz, 2H), 3.88 (t, 0.1=6.6 Hz, 2H), 1.77-1.70 (m, 4H), 1.45-1.31 (m, 5H), 1.28 (s, 12H), 1.25-1.18 (m, 1H), 0.87 (d, J=7.1 Hz, 3H), 0.84-0.73 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 159.01, 138.07, 116.90, 104.99, 82.27, 69.87, 68.15, 48.83, 33.33, 31.77, 29.10, 28.67, 26.20, 15.94. [].sub.D.sup.20=+4.9 (c=0.78, CHCl.sub.3). HPLC (OD-H, 1% IPA in hexanes, 1 mL/min, 220 nm) ee=94%: t.sub.R (minor)=44.3 min, t.sub.R (major)=47.8 min. HRMS (EI) calculated for C.sub.20H.sub.32O.sub.3BI [M].sup.+ 457.1526, found 457.1521.

    [0374] Compound 37k

    ##STR00157##

    [0375] The regioselectivity of the crude product is (Markov:anti-Markov) 84:16, anhydrous oil, yield=60%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.63 (d, J=7.9 Hz, 1H), 7.36 (d, J=8.4 Hz, 1H), 7.20 (t, J=7.6 Hz, 1H), 7.14-7.02 (m, 2H), 6.48 (s, 1H), 4.11 (t, J=7.1 Hz, 2H), 1.89-1.78 (m, 2H), 1.73 (s, 2H), 1.51-1.41 (m, 1H), 1.40-1.29 (m, 3H), 1.27 (s, 12H), 0.90 (d, J=7.0 Hz, 3H), 0.86-0.81 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 135.95, 128.55, 127.79, 121.18, 120.83, 119.02, 109.41, 100.68, 69.94, 48.80, 46.42, 33.07, 31.75, 30.53, 29.73, 28.59, 27.28, 15.97. [].sub.D.sup.20=+7.2 (c=0.23, CHCl.sub.3). HPLC (OD-H, 10% IPA in hexanes, 1 mL/min, 220 nm) ee=98%: t.sub.R (major)=13.1 min, t.sub.R (minor)=14.6 min. HRMS (ESI) calculated for C.sub.21H.sub.33BNO.sub.2 [M+H].sup.+ 341.2635, found 341.2634.

    [0376] Compound 37l

    ##STR00158##

    [0377] The regioselectivity of the crude product is (Markov:anti-Markov) 83:17, anhydrous oil, yield=53%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.75 (d, J=7.7 Hz, 1H), 7.60 (s, 1H), 7.41 (d, J=8.1 Hz, 1H), 7.32 (t, J=7.1 Hz, 1H), 7.27 (t, J=7.3 Hz, 1H), 4.14 (t, J=7.1 Hz, 2H), 2.04-1.77 (m, 2H), 1.71 (s, 2H), 1.48-1.38 (m, 1H), 1.37-1.25 (m, 3H), 1.23 (d, J=3.6 Hz, 12H), 0.87 (d, J=7.0 Hz, 3H), 0.84-0.75 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 135.31, 134.65, 127.93, 123.60, 121.94, 119.87, 116.05, 110.58, 85.26, 69.99, 48.73, 47.27, 32.90, 31.69, 31.68, 30.05, 26.10, 15.96. [].sub.D.sup.20=+11.3 (c=0.54, CHCl.sub.3). HPLC (OD-H, 10% IPA in hexanes, 1 mL/min, 220 nm) ee=94%: t.sub.R (major)=25.3 min, t.sub.R (minor)=27.2 min. HRMS (ESI) calculated for C.sub.22H.sub.35O.sub.2BN.sub.3 [M+NH.sub.4].sup.+ 383.2853, found 383.2853.

    [0378] Compound 37m

    ##STR00159##

    [0379] The regioselectivity of the crude product is (Markov:anti-Markov) 85:15, anhydrous oil, yield=67%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.28-8.06 (m, 1H), 7.82 (s, 1H), 7.38-7.35 (m, 1H), 7.28-7.25 (m, 2H), 4.12 (t, J=7.1 Hz, 2H), 3.90 (s, 3H), 1.94-1.78 (m, 2H), 1.70 (s, 2H), 1.47-1.37 (m, 1H), 1.37-1.25 (m, 3H), 1.23 (d, J=4.1 Hz, 12H), 0.88 (d, J=6.9 Hz, 3H), 0.83-0.77 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 165.51, 136.47, 134.25, 126.72, 122.52, 121.67, 121.64, 110.02, 106.60, 69.94, 50.87, 48.73, 47.06, 32.98, 31.67, 31.66, 30.10, 26.21, 15.94. [].sub.D.sup.20=+15.1 (c=0.70, CHCl.sub.3). HPLC (OJ-H, 10% IPA in hexanes, 1 mL/min, 254 nm) ee=97%: t.sub.R (minor)=22.4 min, t.sub.R (major)=24.0 min. HRMS (ESI) calculated for C.sub.23H.sub.35O.sub.4BN [M+H].sup.+ 399.2690, found 399.2687.

    [0380] Compound 37n

    ##STR00160##

    [0381] The regioselectivity of the crude product is (Markov:anti-Markov) 83:17, anhydrous oil, yield=71%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.65 (d, J=7.8 Hz, 1H), 7.37 (d, J=8.2 Hz, 1H), 7.22 (t, J=7.6 Hz, 1H), 7.10 (d, J=8.3 Hz, 2H), 6.50 (s, 1H), 4.12 (t, J=7.1 Hz, 2H), 1.85 (s, 2H), 1.78 (s, 2H), 1.48-1.10 (m, 18H), 0.91 (d, J=6.9 Hz, 3H), 0.86-0.76 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 135.94, 128.54, 127.79, 121.22, 120.88, 119.08, 109.40, 100.74, 69.93, 48.88, 46.41, 33.31, 31.82, 30.23, 29.73, 28.59, 27.28, 15.98. [].sub.D.sup.20=+2.7 (c=0.26, CHCl.sub.3). HPLC (SFC, OD, 15% IPA in CO.sub.2, 1.3 mL/min, 214 nm) ee=90%: t.sub.R (major)=32.3 min, t.sub.R (minor)=33.4 min. HRMS (ESI) calculated for C.sub.22H.sub.35O.sub.2BN [M+H].sup.+ 355.2792, found 355.2791.

    [0382] Compound 37o

    ##STR00161##

    [0383] The regioselectivity of the crude product is (Markov:anti-Markov) 85:15, yellow oil, yield=43%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.23 (dd, J=5.9, 3.0 Hz, 1H), 7.30-7.27 (m, 1H), 7.25-7.19 (m, 2H), 4.04 (t, J=7.4 Hz, 2H), 2.90 (t, J=6.1 Hz, 2H), 2.59-2.50 (m, 2H), 2.27-2.15 (m, 2H), 1.80-1.70 (m, 2H), 1.68 (s, 2H), 1.47-1.26 (m, 4H), 1.21 (d, 0.1=3.5 Hz, 12H), 0.86 (d, J=7.0 Hz, 3H), 0.81-0.75 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 193.77, 151.46, 136.68, 124.89, 122.78, 122.33, 121.61, 112.52, 109.47, 69.97, 48.72, 43.86, 37.87, 33.01, 31.69, 31.67, 30.03, 26.35, 23.45, 22.33, 15.90. [].sub.D.sup.20=+8.2 (c=0.57, CHCl.sub.3). HPLC (OD-H, 10% IPA in hexanes, 1 mL/min, 220 nm) ee=97%: t.sub.R (major)=45.8 min, t.sub.R (minor)=53.7 min. HRMS (ESI) calculated for C.sub.25H.sub.37O.sub.3BN [M+H].sup.+ 409.2897, found 409.2897.

    [0384] Compound 37p

    ##STR00162##

    [0385] The regioselectivity of the crude product is (Markov:anti-Markov) 82:18, colorless oil, yield=60%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.13 (d, J=7.7 Hz, 2H), 7.54-7.39 (m, 4H), 7.25 (t, J=7.3 Hz, 2H), 4.31 (t, J=7.3 Hz, 2H), 1.91-1.87 (m, 2H), 1.78 (s, 2H), 1.50-1.36 (m, 5H), 1.32 (s, 12H), 1.27-1.15 (m, 1H) 0.93 (d, J=7.0 Hz, 3H), 0.87-0.75 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 140.44, 125.54, 122.80, 120.30, 118.63, 108.69, 69.93, 48.88, 43.10, 33.34, 31.82, 28.90, 28.75, 27.58, 16.02. [].sub.D.sup.20=+3.7 (c=0.22, CHCl.sub.3). HPLC (AD-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=95%: t.sub.R (minor)=17.6 min, t.sub.R (major)=19.1 min. HRMS (ESI) calculated for C.sub.26H.sub.37O.sub.2BN [M+H].sup.+ 405.2948, found 405.2942.

    [0386] Compound 37q

    ##STR00163##

    [0387] The regioselectivity of the crude product is (Markov:anti-Markov) 81:19, colorless oil, yield=44%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 6.65 (s, 2H), 6.13 (s, 2H), 3.85 (t, J=7.3 Hz, 2H), 1.80-1.72 (m, 4H), 1.50-1.32 (m, 4H), 1.30 (s, 12H), 1.26-1.13 (m, 2H), 0.89 (d, J=7.0 Hz, 3H), 0.84-0.73 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 120.43, 107.65, 69.91, 49.63, 48.87, 33.27, 31.80, 31.56, 28.52, 27.03, 15.93. [].sub.D.sup.20=+4.9 (c=0.18, CHCl.sub.3). HPLC (OJ-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=95%: t.sub.R (major)=22.6 min, t.sub.R (minor)=28.6 min. HRMS (ESI) calculated for C.sub.18H.sub.33BNO.sub.2 [M+H].sup.+ 305.2635, found 305.2633.

    [0388] Compound 37r

    ##STR00164##

    [0389] The regioselectivity of the crude product is (Markov:anti-Markov) 86:14, yellow oil, yield=62%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.95 (s, 1H), 7.69 (d, J=8.0 Hz, 1H), 7.40 (d, J=8.5 Hz, 1H), 7.33 (t, J=7.6 Hz, 1H), 7.10 (t, J=7.4 Hz, 1H), 4.35 (t, J=7.1 Hz, 2H), 1.98-1.81 (m, 2H), 1.68 (s, 2H), 1.43 (d, J=8.0 Hz, 1H), 1.37-1.24 (m, 3H), 1.22 (s, 12H), 0.85 (d, J=7.0 Hz, 3H), 0.80-0.73 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 132.48, 125.91, 120.98, 120.21, 109.08, 69.87, 49.04, 48.75, 33.07, 31.70, 30.23, 26.27, 15.89. [].sub.D.sup.20=+25.0 (c=0.60, CHCl.sub.3). HPLC (IA, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=86%: t.sub.R (major)=21.1 min, t.sub.R (minor)=22.4 min. HRMS (ESI) calculated for C.sub.20H.sub.32O.sub.2BN.sub.2 [M+H].sup.+ 342.2588, found 342.2584.0

    [0390] Compound 37s

    ##STR00165##

    [0391] The regioselectivity of the crude product is (Markov:anti-Markov) 85:15, colorless oil, yield=56%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.29 (d, J=4.6 Hz, 1H), 7.86 (d, J=7.7 Hz, 1H), 7.20 (d, J=3.3 Hz, 1H), 7.00 (dd, J=7.5, 4.7 Hz, 1H), 6.40 (d, J=3.2 Hz, 1H), 4.26 (t, J=7.2 Hz, 2H), 1.94-1.77 (m, 2H), 1.69 (s, 2H), 1.49-1.36 (m, 1H), 1.35-1.25 (m, 3H), 1.22 (s, 12H), 0.85 (d, J=7.0 Hz, 3H), 0.81-0.71 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 147.36, 142.51, 128.54, 127.98, 120.55, 115.34, 99.01, 69.88, 48.77, 44.60, 33.10, 31.71, 31.70, 30.70, 26.26, 15.93. [].sub.D.sup.20=+6.8 (c=0.56, CHCl.sub.3). HPLC (OD-H, 10% IPA in hexanes, 1 mL/min, 220 nm) ee=91%: t.sub.R (major)=9.7 min, t.sub.R (minor)=10.5 min. HRMS (ESI), calculated for C.sub.20H.sub.32O.sub.2BN.sub.2 [M+H].sup.+ 342.2588, found 342.2582.

    [0392] Compound 37t

    ##STR00166##

    [0393] The regioselectivity of the crude product is (Markov:anti-Markov) 83:17, colorless oil, yield=53%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 8.13 (d, J=4.3 Hz, 1H), 7.52 (t, J=7.6 Hz, 1H), 6.85-6.77 (m, 1H), 6.69 (d, J=8.3 Hz, 1H), 4.25 (t, J=6.7 Hz, 2H), 1.79-1.71 (m, 4H), 1.48-1.39 (m, 3H), 1.35-1.30 (m, 1H), 1.29 (s, 12H), 0.89 (d, J=6.5 Hz, 3H), 0.86-0.77 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 164.09, 146.82, 138.37, 116.31, 111.06, 69.90, 66.12, 48.83, 33.23, 31.76, 31.55, 29.40, 25.43, 15.91. [].sub.D.sup.20=+6.7 (c=0.42, CHCl.sub.3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 254 nm) ee=90%: t.sub.R (minor)=10.0 min, t.sub.R (major)=11.0 min. HRMS (ESI) calculated for C.sub.18H.sub.31O.sub.3BN [M+H].sup.+ 319.2428, found 319.2423.

    ##STR00167##

    [0394] Compound 37u

    [0395] The regioselectivity of the crude product is (Markov:anti-Markov) 90:10, white power, melting point: 85-86 C., yield=62%, .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.11 (s, 4H), 2.45-2.39 (m, 1H), 2.32 (s, 3H), 2.01-1.67 (m, 10H), 1.52-1.36 (m, 3H), 1.32 (s, 12H), 1.28-0.94 (m, 10H), 0.94-0.68 (m, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 144.95, 135.11, 128.93, 126.67, 69.85, 48.89, 44.26, 43.48, 42.97, 38.28, 37.00, 34.74, 33.79, 33.71, 31.83, 30.97, 30.42, 30.17, 20.99, 16.07. [].sub.D.sup.20=+6.3 (c=0.21, CHCl.sub.3). HPLC (OJ-H, 1% IPA in hexanes, 1 mL/min, 220 nm) ee=96%: t.sub.R(minor)=16.2 min, t.sub.R (major)=18.6 min.

    [0396] Compound 37v

    ##STR00168##

    [0397] The regioselectivity of the crude product is (Markov:anti-Markov) 82:18, colorless oil, yield=50%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 1.76 (s, 2H), 1.42-1.33 (m, 2H), 1.30 (s, 12H), 1.27-1.12 (m, 16H), 0.87 (t, J=6.2 Hz, 6H), 0.83-0.70 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 69.81, 48.88, 33.56, 31.91, 31.77, 29.98, 29.69, 29.67, 29.64, 29.35, 29.04, 22.67, 15.94, 14.08. [].sub.D.sup.20=+4.9 (c=0.41, CHCl.sub.3). The compound is oxidized into alcohol, and reacted with benzoyl chloride to determine the enantioselectivity, HPLC (OD-H, 0.1% IPA in hexanes, 1 mL/min, 220 nm) ee=91% t.sub.R (minor)=7.2 min, t.sub.R (major)=8.0 min. HRMS (EI) calculated for C.sub.19H.sub.39O.sub.2B [M].sup.+09.3079, found 309.3073.

    [0398] Compound 37w

    ##STR00169##

    [0399] The regioselectivity of the crude product is (Markov:anti-Markov) 90:10, colorless oil, yield=78%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.50 (d, J=7.9 Hz, 6H), 7.28 (t, J=7.6 Hz, 6H), 7.18 (t, J=7.2 Hz, 3H), 2.13-2.12 (m, 2H), 1.78 (s, 2H), 1.58-1.37 (m, 4H), 1.32 (s, 12H), 1.27-1.11 (m, 1H), 0.90 (d, J=7.2 Hz, 3H), 0.84-0.74 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 146.49, 128.71, 127.67, 126.06, 70.86, 69.92, 48.88, 44.02, 31.82, 31.12, 30.40, 15.87. [].sub.D.sup.20=+0.9 (c=0.22, CHCl.sub.3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=95%: t.sub.R(minor)=7.4 min, t.sub.R (major)=8.5 min. HRMS (ESI) calculated for C.sub.31H.sub.41O.sub.2BN [M+H].sup.+ 469.3261, found 469.3259.

    [0400] Compound 37x

    ##STR00170##

    [0401] The regioselectivity of the crude product is (Markov:anti-Markov) 88:12, colorless oil, yield=67%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.47 (d, J=8.1 Hz, 6H), 7.29 (t, J=7.6 Hz, 6H), 7.26-7.21 (m, 3H), 3.04 (t, J=6.8 Hz, 2H), 1.78 (s, 2H), 1.67-1.64 in, 2H), 1.56-1.45 in, 1H), 1.31 (s, 12H), 1.29-1.16 (m, 1H), 0.91 (d, 0.1=7.2 Hz, 3H), 0.86-0.78 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 144.67, 128.73, 127.63, 126.70, 86.19, 69.92, 64.32, 48.87, 31.82, 29.94, 29.53, 15.87. [].sub.D.sup.20=+2.1 (c=0.28, CHCl.sub.3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=91%: t.sub.R(minor)=7.5 min, t.sub.R (major)=10.0 min.

    [0402] Compound 37y

    ##STR00171##

    [0403] The regioselectivity of the crude product is (Markov:anti-Markov) 82:18, colorless oil, yield=50%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.67 (d, 0.1=6.8 Hz, 4H), 7.47-7.29 (m, 6H), 3.64 (t, 0.1=6.6 Hz, 2H), 1.75 (s, 2H), 1.61-1.53 (m, 2H), 1.51-1.39 (m, 1H), 1.28 (s, 12H), 1.22-1.17 (m, 1H), 1.04 (s, 9H), 0.88 (d, J=7.0 Hz, 3H), 0.84-0.70 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 135.55, 134.32, 129.35, 127.49, 69.87, 64.58, 48.83, 32.08, 31.77, 29.52, 26.87, 19.23, 15.87. [].sub.D.sup.20=+3.7 (c=0.74, CHCl.sub.3). HPLC (OD-H, 1% IPA in hexanes, 1 mL/min, 220 nm) ee=90%: t.sub.R (minor)=12.7 min, t.sub.R (major)=14.8 min. HRMS (ESI) calculated for C.sub.28H.sub.44O.sub.3BSi [M+H].sup.+ 466.3184, found 466.3183.

    [0404] Compound 37z

    ##STR00172##

    [0405] The regioselectivity of the crude product is (Markov:anti-Markov) 85:15, colorless oil, yield=45%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 3.52 (t, J=6.8 Hz, 2H), 1.82-1.70 (m, 4H), 1.47-1.36 (m, 3H), 1.34-1.11 (m, 17H), 0.88 (d, J=7.0 Hz, 3H), 0.81-0.78 (m, 1H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 69.89, 48.85, 45.24, 33.35, 32.66, 31.78, 29.16, 28.80, 26.89, 15.95. [].sub.D.sup.20=+6.5 (c=0.24, CHCl.sub.3). The compound is oxidized into alcohol, and reacted with benzoyl chloride to determine the enantioselectivity, HPLC (AD-H, 1% IPA in hexanes, 0.5 mL/min, 220 nm) ee=91%: t.sub.R(minor)=10.5 min, t.sub.R (major)=12.6 min. HRMS (EI) calculated for C.sub.15H.sub.30O.sub.2BCl [M].sup.+287.2064, found 287.2071.

    [0406] Compound 37aa

    ##STR00173##

    [0407] The regioselectivity of the crude product is (Markov:anti-Markov) 94:4, colorless oil, yield=83%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.56 (d, J=5.2 Hz, 4H), 7.35 (s, 6H), 1.66 (s, 2H), 1.45 (dd, J=14.7, 8.9 Hz, 1H), 1.25 (s, 12H), 1.09-1.04 (m, 1H), 1.00 (d, J=6.8 Hz, 3H), 0.94 (dd, J=14.6, 4.5 Hz, 1H), 0.58 (s, 3H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 138.45, 138.43, 134.67, 134.60, 128.76, 127.62, 69.91, 48.55, 31.68, 31.62, 20.74, 17.39. [].sub.D.sup.20=+13.1 (c=0.35, CHCl.sub.3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=96%: t.sub.R (minor)=9.8 min, t.sub.R (major)=13.9 min. HRMS (ESI) calculated for C.sub.23H.sub.37O.sub.2BNSi [M+NH.sub.4].sup.+ 397.2717, found 397.2713.

    [0408] Compound 37bb

    ##STR00174##

    [0409] The regioselectivity of the crude product is (Markov:anti-Markov) 87:13, colorless oil, yield=80%; .sup.1H NMR (400 MHz, CDCl.sub.3) : 7.54-7.53 (m, 2H), 7.35-7.34 (m, 3H), 1.78 (s, 2H), 1.47-1.43 (m, 1H), 1.31 (s, 12H), 1.28-1.12 (m, 1H), 0.91-0.83 (m, 4H), 0.78-0.74 (m, 2H), 0.26 (s, 6H); .sup.13C NMR (101 MHz, CDCl.sub.3) : 140.11, 133.59, 128.56, 127.59, 69.89, 48.90, 31.83, 27.51, 15.74, 14.89. [].sub.D.sup.20=+6.2 (c=0.26, CHCl.sub.3). HPLC (OD-H, 5% IPA in hexanes, 1 mL/min, 220 nm) ee=94%: t.sub.R (major)=6.4 min, t.sub.R(minor)=7.5 min. HRMS (ESI) calculated for C.sub.19H.sub.37BNO.sub.2Si [M+NH.sub.4].sup.+ 349.2717, found 349.2711.

    [0410] Although the specific embodiments of this present invention are described above, those skilled in the art should understand that these are merely examples, and without departing from the principle and essence of the invention, various changes or modifications can be made to these embodiments. Therefore, the scope of protection of this present invention is defined by the appended claims.