PROCESS FOR PREPARING DIMERIC PHOSPHAZENE DERIVED BRØNSTED ACIDS

Abstract

The present invention describes a new synthesis to chiral imidodiphosphoryl compounds, their salts, metal complexes as well as derivatives thereof. Said chiral imidodiphosphoryl compounds can be used as catalysts for Brnsted acid/Brnsted base or Lewis acid/Lewis base mediated transformations.

Claims

1. Process for preparing a chiral imidodiphosphoryl compound of formula (I) or a tautomeric or ionic form thereof: ##STR00047## wherein in formula (I): X is the same or different on each P and represents O, S, Se, CR.sup.C.sub.2 or NR.sup.C, Z.sup.1 to Z.sup.4 are, independently from each other, the same or different and each represents O, S, Se or NR.sup.C, each n is, independently from each other, the same or different and stands for 0 or 1, W is selected from hydrogen, halogen, a metal selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Se, Te, La, Sm, Eu, Yb, U or a cationic organic group, a substituted borane BR.sup.IR.sup.IIR.sup.III or a substituted silicon SiR.sup.IR.sup.IIR.sup.III, wherein R.sup.I , R.sup.II and R.sup.III may be same or different and each stands for hydrogen, halogen, an optionally O bonded C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbon, optionally having one or more unsaturated bonds or one or more hetero atoms in the chain, a C.sub.5 to C.sub.18 heteroaromatic hydrocarbon, a C.sub.6 to C.sub.18 aromatic hydrocarbon or partially arene-hydrogenated forms thereof, each hydrocarbon optionally being substituted by one or more groups selected from C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbons, or one or more heterosubstituents, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are, independently from each other, the same or different and each represents an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, heteroaromatic hydrocarbon group, and, for n=O, F, Cl, Br, I, CN, OTf, OMs, OTs, or any other pseudohalogenide with leaving group properties, whereby R.sup.1 may form a bond with any one of R.sup.2, R.sup.3 or R.sup.4 and the other two of R.sup.2, R.sup.3 or R.sup.4 may form a bond with each other, or whereby any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, X.sup.1 and X.sup.2 may form a bond with each other, when R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each represent an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, heteroaromatic hydrocarbon group; R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, an heteroaromatic hydrocarbon group, or R.sup.N; with the proviso that at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4 or R.sup.C represents a hydrocarbon group as defined before, each hydrocarbon group optionally being further substituted by one or more heterosubstituents, aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group or heteroaromatic hydrocarbon group, R.sup.N is an electron withdrawing or electron donating group, being the same or different on each position and being selected from: i. -alkyl, CO-alkyl, (CO)O-alkyl, sulfinyl alkyl, sulfonyl alkyl, sulfonyl iminoalkyl, sulfonyl bisiminoalkyl, phosphinyl dialkyl, phosphonyl alkyl, alkyl phosphorane, N,N-alkylimidazolidin-2-iminyl wherein alkyl is a C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino NH, substituted imino NR.sup.C, amino NH.sub.2, or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group or an heteroaromatic hydrocarbon group; ii. -aryl, CO-aryl, (CO)O-aryl, sulfinyl aryl, sulfonyl aryl, sulfonyl iminoaryl, sulfonyl iminosulfonylaryl, sulfonyl bisiminoaryl, phosphinyl diaryl, phosphinyl alkylaryl, phosphonyl aryl, aryl phosphoranes, aryl alkyl phosphoranes, N,N-arylimidazolidin-2-iminyl, N-aryl-N-alkylimidazolidin-2-iminyl wherein aryl is a C.sub.6 to C.sub.18 aromatic hydrocarbon, optionally having at least one substituent selected from halogen, a C.sub.1 to C.sub.6 aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, preferably F and/or Cl, cyano, nitro, imino NH, substituted imino NR.sup.C, amino NH.sub.2 or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group; iii. -heteroaryl, CO-heteroaryl, (CO)O-heteroaryl, sulfinyl heteroaryl, sulfonyl heteroaryl, (PO)-di-heteroaryl, phosphinyl diheteroaryl, phosphinyl arylheteroaryl, phosphinyl heteroaryl alkyl, phosphonyl heteroaryl, heteroaryl phosphoranes, heteroaryl aryl phosphoranes, heteroaryl aryl alkyl phosphoranes, N,N-heteroarylimidazolidin-2-iminyl, N-heteroaryl-N-alkylimidazolidin-2-iminyl, N-heteroaryl-N-arylimidazolidin-2-iminyl wherein heteroaryl is a C.sub.2 to C.sub.18 heteroaromatic hydrocarbon, optionally having at least one substituent selected from halogen, a C.sub.1 to C.sub.6 aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino NH, substituted imino NR.sup.C, amino NH.sub.2, or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group-; whereby for those groups of i.), ii.) and iii.) having at least one CO, SO or PO moiety, O may be replaced by an imino group NR, and/or for those groups of i.), ii.) and iii.), having at least one COR, SOR or POR moiety, OR may be replaced by an amino group NRR, wherein R and R, independently from each other, represent an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group,, said process comprising the steps of reacting, in at least one reaction step, a bisphosphazene compound of formula (II):
Q.sub.3PN.sup.+PQ.sub.3 A.sup.(II) wherein in formula (II): each Q is, independently from each other, the same or different, and represents F, Cl, Br, I, CN, OTf, OMs, OTs, or any other pseudohalogenide with leaving group properties, and wherein A.sup. represents a halogenide or weakly coordinating anion, with one to six nucleophilic groups being present on one to six, optionally chiral, compounds: wherein one or two nucleophilic groups X.sup.W which can be the same or different from each other and which are present on one to two optionally chiral bivalent compounds of formula (III) X.sup.WW.sub.2, wherein X.sup.W has the meaning of any of O, S, Se, CR.sup.C.sub.2, or NR.sup.C, wherein R.sup.C and W have the meanings as defined above, wherein up to four nucleophilic groups Z.sup.W, which can be the same or different from each other, are present on one to four optionally chiral monovalent compounds of formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined above, Z.sup.W is the same or different on each compound and has the meaning of any of Z.sup.1 to Z.sup.4; and W and n have the meanings as defined above, wherein at least one nucleophilic group X.sup.W being present on one to two optionally chiral bivalent compounds of formula (III) X.sup.WW.sub.2, wherein X.sup.W has the meaning of any of CR.sup.C.sub.2 or NR.sup.C; wherein R.sup.C has the meaning as defined above, or at least one nucleophilic groups Z.sup.W being present on one to four optionally chiral monovalent compounds of formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined above; Z.sup.W, W and n have the meaning as defined above, is reacted with the compound of formula (II), with the proviso that, in formula (I), at least one of R.sup.1 to R.sup.4 is chiral, or at least two of R.sup.1 to R.sup.4 form a chiral group, or at least one P or at least one S is chiral.

2. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 1, wherein in a first reaction step, one nucleophilic group X.sup.W which has the meaning of X as defined in claim 1, and which is present on one optionally chiral compound of formula (III) X.sup.WW.sub.2 or two nucleophilic groups X.sup.W which have the meaning of X as defined in claim 1, and which are present on one or on two optionally chiral compounds of formula (III) X.sup.WW.sub.2, respectively, are reacted with a bisphosphazene compound of formula (II), and, in a second step, the reaction product obtained in the first reaction step is optionally reacted with a quencher for removing any remaining Q group, or with up to four nucleophilic groups Z.sup.W which can be the same or different from each other and which are present on one to four optionally chiral compounds of formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined in claim 1, Z.sup.W is the same or different and has the meaning of any of Z.sup.1 to Z.sup.4 , W has the meaning as defined in claim 1 and n is 0 or 1, are reacted with the reaction product of the first step, whereby the reaction product obtained in the second step is optionally reacted with a quencher for removing any remaining Q group, wherein Z.sup.1 to Z.sup.4, and Q have the meanings as defined in claim 1.

3. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 1, wherein in a first reaction step, one to four nucleophilic groups Z.sup.W, which can be the same or different from each other and which are present on one to four optionally chiral compounds of the formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined in claim 1, Z.sup.W is the same or different and has the meaning of any of Z.sup.1 to Z.sup.4, W has the meaning as defined in claim 1 and n is 0 or 1, are reacted with the bisphosphazene compound of the general formula (II), and, optionally in a second step, one nucleophilic group X.sup.W which has the meaning of X as defined in claim 1 and which is present on one optionally chiral compound of formula (III) X.sup.WW.sub.2 or two nucleophilic groups X.sup.W which have the meaning of X as defined in claim 1, and which are present on one or two optionally chiral compounds of formula (III) X.sup.WW.sub.2, respectively, are reacted with the reaction product of the first reaction step, and, when in the second step, one nucleophilic group X.sup.W present on one optionally chiral compound of formula (III) X.sup.WW.sub.2 is reacted with the reaction product obtained in the first step, the reaction product obtained in the second step is optionally reacted with a quencher for removing the remaining Q group, wherein Z.sup.1 to Z.sup.4 and Q have the meanings as defined in claim 1.

4. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 1, wherein in a first reaction step, four nucleophilic groups Z.sup.W, which can be the same or different from each other and which are present on two to four optionally chiral compounds of formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined in claim 1, Z.sup.W is the same or different and has the meaning of any of Z.sup.1 to Z.sup.4, W has the meaning as defined in claim 1 and n is 0 or 1, are reacted with the bisphosphazene compound of formula (II), and, in a second reaction step, the reaction product obtained in the first step is optionally reacted with a quencher for removing the remaining Q groups, wherein Z.sup.1 to Z.sup.4 and Q have the meanings as defined in claim 1.

5. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 1, wherein two nucleophilic groups X.sup.W on the compound of formula (III) X.sup.WW.sub.2 , wherein W has the meaning as defined in claim 1, which are CR.sup.C.sub.2 or NR.sup.C and four nucleophilic groups Z.sup.W on the compound of formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined in claim 1, Z.sup.W is the same or different and has the meaning of any of Z.sup.1 to Z.sup.4, W has the meaning as defined in claim 1 and n is 0 or preferably 1, are present on one optionally chiral compound and are stepwise reacted with the bisphosphazene compound of formula (II), wherein Z.sup.1 to Z.sup.4 and Q have the meanings as defined in claim 1.

6. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 1, wherein four nucleophilic groups Z.sup.W, which can be the same or different from each other and which are present on two optionally chiral compounds of formula (IV) R.sup.CZ.sup.W.sub.nW, wherein R.sup.C has the meaning as defined in claim 1, Z.sup.W is the same or different and has the meaning of any of Z.sup.1 to Z.sup.4, W has the meaning as defined in claim 1 and n is 0 or 1, are reacted with the bisphosphazene compound of formula (II),
Q.sub.3PN.sup.+PQ.sub.3 A.sup.(II) wherein in formula (II): each Q is, independently from each other, the same or different, and represents F, Cl, Br, I, CN, OTf, OMs, OTs, or any other pseudohalogenide with leaving group properties, and wherein A.sup. represents a halogenide or weakly coordinating anion, wherein said two optionally chiral compounds of formula (IV) R.sup.CZ.sup.W.sub.nW, which may be the same or different, are each represented by a structural unit of formula (V): ##STR00048## wherein Z.sup.1, Z.sup.2, Z.sup.3, Z.sup.4, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 have the meanings as defined in claim 1.

7. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 6, wherein said structural unit of formula (V) is the same or different and is represented by BINOL, VANOL, VAPOL, TADDOL, SPINOL, or comprises, as Z.sup.1,3R.sup.1,3R.sup.2,4Z.sup.2,4, 1,1binaphthyl, 8H-1,1-binaphthyl, biphenyl, 3,3-(diphenyl)-2,2-binaphthyl, biphenyl, 2,2-diphenyl-3,3-biphenanthrenyl, 1,1-bianthracenyl, 1,1-biphenanthryl or partially arene-hydrogenated forms thereof, 2,2-dimethyl-1,3-dioxolanyl, a C.sub.2 to C.sub.18 alkyl chain, spirobiindanyl, tetrahydrospirobinaphthalenyl, paracyclophanyl, metallocenyl, wherein W is H, wherein each of the compounds before is optionally substituted by one or more substituents which may be same or different on each position and which is each selected from hydrogen, a heterosubstituent, a C.sub.1 to C.sub.20 aliphatic hydrocarbon, optionally having one or more unsaturated bonds, a C.sub.6 to C.sub.18 aromatic hydrocarbon or a C.sub.5 to C.sub.18 heteroaromatic hydrocarbon which hydrocarbons may be substituted by one or more heterosubstituents.

8. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 1, wherein said one or two optionally chiral compounds of formula (III) X.sup.WW.sub.2, which may be the same or different, are represented by R.sup.NNH.sub.2, wherein R.sup.N has the meaning as defined in claim 1.

9. Process for preparing a chiral imidodiphosphoryl compound of formula (I) as claimed in claim 7, wherein said structural unit of formula (V) is the same or different and is represented by formula (VI), the partially arene-hydrogenated forms thereof or by formula (VII): ##STR00049## wherein in said formulae (VI) and (VII), the substituent R may be same or different on each position and is each selected from hydrogen, a heterosubstituent, a C.sub.1 to C.sub.20 aliphatic hydrocarbon, optionally having one or more unsaturated bonds, a C.sub.6 to C.sub.18 aromatic hydrocarbon or a C.sub.5 to C.sub.18 heteroaromatic hydrocarbon which hydrocarbons may be substituted by one or more heterosubstituents, and two of which substituents R may form an aliphatic or aromatic ring system with each other and wherein Z.sup.W and W are as defined in claim 1.

10. A chiral imidodiphosphoryl compound of formula (I): ##STR00050## wherein in formula (I): X is the same or different on each P and represents O, S, Se, CR.sup.C.sub.2 or NR.sup.C, Z.sup.1 to Z.sup.4 are, independently from each other, the same or different and each represents O, S, Se or NR.sup.C, each n is, independently from each other, the same or different and stands for 0 or 1, W is selected from hydrogen, halogen, a metal selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Ge, Sn, Pb, As, Sb, Bi, Se, Te, La, Sm, Eu, Yb, U or a cationic organic group, a substituted borane BR.sup.IR.sup.IIR.sup.III or a substituted silicon SiR.sup.IR.sup.IIR.sup.III, wherein R.sup.I, R.sup.II and R.sup.III may be same or different and each stands for hydrogen, halogen, an optionally O bonded C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbon, optionally having one or more unsaturated bonds or one or more hetero atoms in the chain, a C.sub.5 to C.sub.18 heteroaromatic hydrocarbon, a C.sub.6 to C.sub.18 aromatic hydrocarbon or partially arene-hydrogenated forms thereof, each hydrocarbon optionally being substituted by one or more groups selected from C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbons, or one or more heterosubstituents, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are, independently from each other, the same or different and each represents an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, heteroaromatic hydrocarbon group, and, for n=0, F, Cl, Br, I, CN, OTf, OMs, OTs, or any other pseudohalogenide with leaving group properties, whereby R.sup.1 may form a bond with any one of R.sup.2, R.sup.3 or R.sup.4 and the other two of R.sup.2, R.sup.3 or R.sup.4 may form a bond with each other, or whereby any of R.sup.1, R.sup.2, R.sup.3, R.sup.4, X.sup.1 and X.sup.2 may form a bond with each other, when R.sup.1, R.sup.2, R.sup.3 and R.sup.4 each represent an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, heteroaromatic hydrocarbon group; R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, an heteroaromatic hydrocarbon group, or R.sup.N; with the proviso that at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4 or R.sup.C represents a hydrocarbon group as defined before, each hydrocarbon group optionally being further substituted by one or more heterosubstituents, aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group or heteroaromatic hydrocarbon group, R.sup.N is an electron withdrawing or electron donating group, being the same or different on each position and being selected from: i. -alkyl, CO-alkyl, (CO)O-alkyl, sulfinyl alkyl, sulfonyl alkyl, sulfonyl iminoalkyl, sulfonyl bisiminoalkyl, phosphinyl dialkyl, phosphonyl alkyl, alkyl phosphorane, N,N-alkylimidazolidin-2-iminyl wherein alkyl is a C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino NH, substituted imino NR.sup.C, amino NH.sub.2, or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group or an heteroaromatic hydrocarbon group; ii. -aryl, CO-aryl, (CO)O-aryl, sulfinyl aryl, sulfonyl aryl, sulfonyl iminoaryl, sulfonyl iminosulfonylaryl, sulfonyl bisiminoaryl, phosphinyl diaryl, phosphinyl alkylaryl, phosphonyl aryl, aryl phosphoranes, aryl alkyl phosphoranes, N,N-arylimidazolidin-2-iminyl, N-aryl-N-alkylimidazolidin-2-iminyl wherein aryl is a C.sub.6 to C.sub.18 aromatic hydrocarbon, optionally having at least one substituent selected from halogen, a C.sub.1 to C.sub.6 aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino NH, substituted imino NR.sup.C, amino NH.sub.2 or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group; iii. -heteroaryl, CO-heteroaryl, (CO)O-heteroaryl, sulfinyl heteroaryl, sulfonyl heteroaryl, (PO)-di-heteroaryl, phosphinyl diheteroaryl, phosphinyl arylheteroaryl, phosphinyl heteroaryl alkyl, phosphonyl heteroaryl, heteroaryl phosphoranes, heteroaryl aryl phosphoranes, heteroaryl aryl alkyl phosphoranes, N,N-heteroarylimidazolidin-2-iminyl, N-heteroaryl-N-alkylimidazolidin-2-iminyl, N-heteroaryl-N-arylimidazolidin-2-iminyl wherein heteroaryl is a C.sub.2 to C.sub.18 heteroaromatic hydrocarbon, optionally having at least one substituent selected from halogen, a C.sub.1 to C.sub.6 aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino NH, substituted imino NR.sup.C, amino NH.sub.2, or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group; whereby for those groups of i.), ii.) and iii.) having at least one CO, SO or PO moiety, O may be replaced by an imino group NR, and/or for those groups of i.), ii.) and iii.), having at least one COR, SOR or POR moiety, OR may be replaced by an amino group NRR, wherein R and R, independently from each other, represent an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group, or a tautomeric or ionic form thereof, obtained according to a process as claimed in claim 1.

11. A chiral imidodiphosphoryl compound of formula (I) or a tautomeric or ionic form thereof according to claim 10: ##STR00051## wherein in formula (I): X is the same or different on each P and represents NR.sup.C, wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, an heteroaromatic hydrocarbon group, or R.sup.N, wherein R.sup.N represents an electron donating substituent, whereby for those groups of i.), ii.) and iii.) having at least one CO, SO or PO moiety, O is replaced by an imino group NR, and/or for those groups of i.), ii.) and iii.), having at least one COR, SOR or POR moiety, OR is replaced by an amino group NRR, wherein R and R, independently from each other, represent an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, an heteroaromatic hydrocarbon group. or RN, whereby RN is selected from: i. -alkyl, CO-alkyl, (CO)O-alkyl, sulfinyl alkyl, sulfonyl alkyl, sulfonyl iminoalkyl, sulfonyl bisiminoalkyl, phosphinyl dialkyl, phosphonyl alkyl, alkyl phosphorane, N,N-alkylimidazolidin-2-iminyl wherein alkyl is a C.sub.1 to C.sub.20 straight chain, branched chain or cyclic aliphatic hydrocarbon, optionally having at least one substituent selected from imino NH, substituted imino NR.sup.C, amino NH.sub.2, or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group; ii. -aryl, CO-aryl, (CO)O-aryl, sulfinyl aryl, sulfonyl aryl, sulfonyl iminoaryl, sulfonyl iminosulfonylaryl, sulfonyl bisiminoaryl, phosphinyl diaryl, phosphinyl alkylaryl, phosphonyl aryl, aryl phosphoranes, aryl alkyl phosphoranes, N,N-arylimidazolidin-2-iminyl, N-aryl-N-alkylimidazolidin-2-iminyl wherein aryl is a C.sub.6 to C.sub.18 aromatic hydrocarbon, optionally having at least one substituent selected from a C.sub.1 to C.sub.6 aliphatic hydrocarbon, optionally having at least one substituent selected from imino NH, substituted imino NR.sup.C, amino NH.sub.2 or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group; iii. -heteroaryl, CO-heteroaryl, (CO)O-heteroaryl, sulfinyl heteroaryl, sulfonyl heteroaryl, (PO)-di-heteroaryl, phosphinyl diheteroaryl, phosphinyl arylheteroaryl, phosphinyl heteroaryl alkyl, phosphonyl heteroaryl, heteroaryl phosphoranes, heteroaryl aryl phosphoranes, heteroaryl aryl alkyl phosphoranes, N,N-heteroarylimidazolidin-2-iminyl, N-heteroaryl-N-alkylimidazolidin-2-iminyl, N-heteroaryl-N-arylimidazolidin-2-iminyl wherein heteroaryl is a C.sub.2 to C.sub.18 heteroaromatic hydrocarbon, optionally having at least one substituent selected from a C.sub.1 to C.sub.6 aliphatic hydrocarbon, optionally having at least one substituent selected from imino NH, substituted imino NR.sup.C, amino NH.sub.2, or substituted amino NHR.sup.C, NR.sup.C.sub.2 wherein R.sup.C represents, independently from each other, an aliphatic hydrocarbon group, a heteroaliphatic hydrocarbon group, an aromatic hydrocarbon group, or an heteroaromatic hydrocarbon group.

12. (canceled)

13. A process comprising conducting a Brnsted acid/Brnsted base or Lewis acid/Lewis base mediated transformation in the presence of a catalyst, wherein the catalyst is a chiral imidodiphosphoryl compound of formula (I) or a tautomeric or ionic form thereof according to claim 10.

14. A process comprising: (a) preparing a chiral imidodiphosphoryl compound of formula (I) or a tautomeric or ionic form thereof according to a process as claimed in claim 1; and (b) conducting a Brnsted acid/Brnsted base or Lewis acid/Lewis base mediated transformation in the presence of a catalyst, wherein the catalyst is the chiral imidodiphosphoryl compound of formula (I) or a tautomeric or ionic form prepared in (a).

Description

[0137] In the Figures:

[0138] FIG. 1 generally describes the inventive synthesis pathway and properties of imidodiphosphoryl-derived Brnsted acids;

[0139] FIGS. 2A-C illustrate the inventive reaction scheme in more detail;

[0140] FIGS. 3A-B compare the results of the inventive synthesis and the previous strategies;

[0141] FIG. 4 illustrates some of the compounds of formula (VI) and (VII) being particularly useful in the inventive process;

[0142] FIGS. 5A-C illustrate some of the groups RN being particularly useful in the inventive process.

EXPERIMENTAL

Example 1: Synthesis of (Trimethylsilyl)Phosphorimidoyl Trichloride

[0143] ##STR00017##

[0144] A 500 mL flame dried two necked round bottom flask with dropping funnel was charged with diethylether (200 mL), hexamethyldisilazane (12.5 mL, 60 mmol), cooled to 0 C. (ice bath) followed by the addition of n-butyllithium (24 mL (2.5 M in hexanes), 60 mmol) within 5 minutes at 0 C. The solution was stirred additional 30 minutes at 0 C. and was then allowed to warm to r.t. forming a colorless suspension. The suspension was cooled again to 0 C. (ice bath) followed by the dropwise addition of phosphorous trichloride (5.2 mL, 60 mmol) within 2 minutes. The cooling bath was removed after full addition of phosphorous trichloride and the milky reaction mixture was allowed to warm to r.t. and stirred for additional 30 minutes at r.t. The milky suspension was cooled to 0 C. (ice bath) followed by the dropwise addition of sulfuryl chloride (6 mL, 60 mmol). The colorless suspension was warmed to r.t. again and stirred additional 60 minutes at r.t. followed by inert filtration over a pad of previously dried pad a celite (schlenk frit, height 3 cm of celite) to obtain a colorless filtrate which was carefully concentrated (130 mbar to 30 mbar) at 0 C. under inert conditions. The resulting highly viscous oil was then purified by bulb to bulb distillation under static vacuum (5 mbar, 25 to 40 C.) condensing the desired product 78 C. (Trimethylsilyl)phosphorimidoyl trichloride was isolated as a colorless viscous oil (12 g, 89%).

[0145] Procedure is based on the reference: Inorg Chem. 2002, 41, 1690

Example 2A: Synthesis of Hexachlorobisphosphazonium Hexachlorophosphate (HCCP)

[0146] PCl.sub.6.sup.

Cl.sub.3PN.sup.+PCl.sub.3

[0147] A flame dried 100 mL Schlenk tube was charged with phosphorous pentachloride (16.6 g, 79.8 mmol) followed by the addition of a solution of (trimethylsilyl)phosphorimidoyl trichloride in dichloromethane (25 mL) at 0 C. to form a colorless suspension which was stirred 2.5 h at room temperature. Additional dichloromethane (20 mL) was added followed by inert filtration. The colorless precipitate was washed two times with dichloromethane (40 mL each) and dried in high vacuum (1*10.sup.3 mbar) for 5 hours to obtain the desired product, as a colorless powder (15.4 g, 72%).

[0148] The procedure is based on reference Inorganic Chemistry, 2004, 43, 2765

Example 2B: Alternative One-Step Synthesis of Hexachlorobisphosphazonium Hexachlorophosphate (HCPP)

[0149] PCl.sub.6.sup.

Cl.sub.3PN.sup.+PCl.sub.3

[0150] A 250 ml two necked round bottom flask, equipped with a reflux condenser and sulfuric acid filled gas bubbler, was flame-dried under argon. The flask was charged with PCl.sub.5 (53.0 g, 254 mmol, 1 equiv.), NH.sub.4Cl (4.31 g, 80.6 mmol, 0.95 equiv.) and suspended in nitrobenzene (80 ml). The suspension was heated 5.5 h to 130 C. Within the first 3 h a constant gas development was observed, whereas the gas development slowly ceased after that time and most of the solid dissolved during the reaction progress (Note: sublimed PCI5 was re-dissolved into the reaction mixture by carefully shaking the glass apparatus). The hot reaction mixture was filtered under inert conditions (argon overpressure through filter paper fitted PE-tube) into a 100 ml Schlenk-flask. Upon cooling to r.t., a colorless precipitate formed from the filtrate. The suspension was left o.n. at r.t. and filtered under inert reaction conditions (argon overpressure through filter paper fitted PE-tube). The beige solid was extensively washed with dry hexanes until the filtrates remain colorless and additionally washed with DCM (100 ml) to afford the desired product as a colorless solid (62%, 28.3 g, 53.2 mmol).

[0151] The procedure is based on reference Anorg. Allg. Chem. 1977, 433, 229

Example 3: Synthesis of Hexachlorobisphosphazonium Chloride

[0152] Cl.sup.

Cl.sub.3PN.sup.+PCl.sub.3

[0153] A flame dried 25 mL schlenk flask was charged with hexachlorobisphosphazonium hexachlorophosphate (2.29 g, 4.30 mmol) and suspended in DCM (30 mL). 4-Dimethylaminopyridine (552 mg, 4.52 mmol, 1.05 equiv.) was added in one portion resulting in the formation of a yellowish solution, of which a colorless precipitate formed within stirring for 5 minutes. The resulting colorless solution was stirred additional 1 h at r.t. followed by cooling in an ice bath. The stirring was stopped and the suspension filtered under inert conditions and the colorless precipitate washed with additional DCM (220 mL) and dried in high vacuum to furnish the desired product as a colorless solid (73%, 1.02 g, 3.14 mmol) Procedure is based on reference Inorganic Chemistry, 2004, 43, 2765

Example 4: Synthesis of Hexachlorobisphosphazonium Hexachloroantimonate

[0154] SbCl.sub.6.sup.

Cl.sub.3PN.sup.+PCl.sub.3

[0155] A flame dried 100 mL schlenk flask was charged with hexachlorobisphosphazonium hexachlorophosphate (1.99 g, 3.74 mmol), suspended in DCM (40 mL) and cooled in an acetone/dry ice bath. A second flame dried 25 mL schlenk flask was charged with SbCl.sub.5 (1.18 g, 3.94 mmol, 1.05 equiv.), diluted with DCM (10 mL) and the resulting solution dropwise transferred to the first pre-cooled schlenk via a polyethylene tubing with argon over pressure (1.2 bar). Upon full addition of SbCl5 the formed suspension was stirred 1 h at 78 C. and additional 3 h at r.t. The suspension was filtered under inert conditions and the colorless precipitate washed with additional DCM (10 mL) followed by drying in high vacuum to furnish the desired product as a colorless solid (69%, 1.61 g, 2.59 mmol)

Example 5: Synthesis of Hexachlorobisphosphazonium Tetrachloroborate

[0156] BCl.sub.4.sup.

Cl.sub.3PN.sup.+PCl.sub.3

[0157] A flame dried 25 mL schlenk flask was charged with hexachlorobisphosphazonium hexachlorophosphate (537 mg, 1.01 mmol), suspended in DCM (10 mL). Boron trichloride (1M in heptane, 1.2. mL, 1.19 equiv.) was added. Upon full addition the formed solution was stirred additional 30 min at r.t., followed by concentration of the solution to a total volume of ca. 5 mL to form a suspension. Additional n-hexane (15 mL) was added and the suspension filtered under indert conditions. The colorless precipitate was washed with additional n-hexane (210 mL) and the colorless solid dried in high vacuum to furnish the desired product as a colorless solid (64% yield, 285 mg, 646 mol).

[0158] Example 6: Synthesis of (S,S)-4-chloro-N-(4-chloro-2,6-diphenyl-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ylidene)-2,6-diphenyl-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-iminium Chloride

##STR00018##

[0159] A flame dried 5 mL schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (2, 310 mg, 0.58 mmol) and (S)-3,3-diphenyl-[1,1-binaphthalene]-2,2-diol (510 mg, 1,64 mmol) followed by the addition of anhydrous pyridine (10 mL). The slightly yellow reaction mixture was stirred additional 20 minutes at r.t. followed by removal of all volatile compounds in high vacuum (1*10.sup.3 mbar) to obtain a beige precipitate which was re-suspended in ethyl acetate (20 mL). The organic phase was removed via inert filtration and the resulting colorless precipitate was dried in high vacuum (1*10.sup.3 mbar) to obtain the desired product (538 mg, 87%).

Example 7: Stepwise Chloride Substitution

[0160] ##STR00019##

[0161] A 10 mL flame dried schlenk tube was charged with hexachlorobisphosphazonium chloride (155 mg, 479 mol, 1 equiv.) and N,N-(amino(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethane-sulfonamide) (402 mg, 959 mol, 2 equiv.). DCM (1 mL) was added and the resulting suspension stirred (100 rpm) for 1 h until gas evolution ceased and the suspension turned into a slightly orange solution. An aliquote was analyzed by .sup.31P-NMR, indicating the characteristic signals of the mono addition product (.sup.31P NMR (203 MHz, CD.sub.2 Cl.sub.2) 9.36 (d, .sup.2J=31.5 Hz), 5.78 (d, .sup.2J=31.5 Hz). Additional DCM (2 mL) was added followed by dropwise addition of NEt.sub.3 (133 l, 0.96 mmol, 2 equiv.). The reaction was stirred for 1 h at r.t. and analyzed by .sup.31P-NMR, indicating the formation of the desired double addition product (.sup.31P NMR (203 MHz, CD.sub.2Cl.sub.2) 10.39 (s)). All volatiles were removed in vacuo. Toluene (4 mL) and (S)-Phenyl-BINOL (210 mg, 480 mol, 1 equiv.) was added followed by subsequent addition of NEt.sub.3 (300 l, 2.16 mmol, 4.5 equiv.). The reaction was stirred 16 h at 90 C., analyzed by .sup.31P-NMR ((203 MHz, CD.sub.2Cl.sub.2) 8.52 (d, .sup.2J=60.2 Hz), 13.90 (d, .sup.2J=60.2 Hz)) and mass-spectroscopy, indicating the formation of the depicted compound as a crude product with a 31 P-NMR purity of ca. 84%.

Example 8: Synthesis of 3,3-Bis(9-anthracenyl)IDP

[0162] ##STR00020##

[0163] A flame dried 5 mL schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (41 mg, 77 mol), (S)-3,3-di(anthracen-9-yl)-[1,1-binaphthalene]-2,2-diol (98.4 mg, 154 mol) followed by the addition of pyridine (1 mL). The suspension was stirred for 15 minutes at r.t. followed by the addition of distilled water (250 l, 13.8 mmol) via a Pasteur pipette and was stirred additional 17 h at 50 C. After cooling to r.t. the reaction mixture was poured into saturated NaHCO.sub.3 solution and extracted with dichloromethane. The combined organic phase was dried over sodium sulfate, concentrated in vacuo and purified by flash column chromatography (dichloromethane) to afford a colorless solid which was acidified with aqueous 6 M HCl. The solid was dissolved in a small quantitiy of dichloromethane and precipitated with hexanes. After decantation of the organic phase the desired product was obtained as a colorless powder (90 mg, 85%).

Example 9: Synthesis of (S,S)-4-(((2r)-4-oxido-2,6-bis(2,4,6-tripentylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(2,4,6-tripentylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine 4-oxide

[0164] ##STR00021##

[0165] A flame dried 10 mL schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (156 mg, 293 mol) and a solution of (S)-3,3-bis(2,4,6-tripentylphenyl)-[1,1-binaphthalene]-2,2-diol in pyridine (5 mL). The slightly yellow suspension was stirred for 24 h at r.t. followed by the addition of distilled water (1 mL). The solution was stirred additional 24 h at r.t. followed by the addition of aqueous HCl (6 M, 20 mL) and dichloromethane (20 mL). The aqueous phase was extracted three times with dichloromethane (20 mL each). The combined organic phase was dried over sodium sulfate and concentrated to dryness to afford a colorless oil which was further purified by flash column chromatography (gradient, hexanes then dichloromethane/hexanes (1:4)) to obtain the desired product as a colorless oil. This oil was dissolved in a small quantitiy of dichloromethane and was washed with aqueous HCl (6 M) to obtain the desired product as a colorless solid (381 mg, 71%).

Example 10: Synthesis of (S,S)-4-(((2r)-4-oxido-2,6-bis(2,4,6-trihexylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(2,4,6-trihexylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine 4-oxide

[0166] ##STR00022##

[0167] A 10 mL flame dried and argonated schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (46 mg, 86.4 mol) and dissolved in a solution of (S)-(o,o,p-tri(n-hexyl)phenyl)BINOL (163 mg, 0.17 mmol 2 equiv. in 1,5 mL pyridine). The reaction was stirred for 19 h at r.t. followed by the addition of water (300 l, 16.6 mmol, 192 equiv.) and stirred additional 5 h at 80 C. until .sup.31P-NMR analysis shows clean hydrolysis to the desired product. After cooling to r.t. the reaction mixture was poured into 30 mL HCl.sub.(aq) and extracted with DCM (330 mL). The combined organic phases were dried over sodium sulfate, concentrated to dryness and purified by FCC (Biotage, gradient: hexanes up to hexanes/DCM (1:1)) to elute the desired product as a salt. Acidification was carried out by dissolving the salt in DCM (3 mL) and HCl.sub.(aq) (6M, 3 mL). The organic phase was isolated, concentrated to dryness followed by drying o.n. in h.v. to furnish the desired product as a colorless viscous oil (78%, 172 mg).

Example 11: Synthesis of (S,S)-4-(((2r)-4-oxido-2,6-bis(2,4,6-triheptylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(2,4,6-triheptylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine 4-oxide

[0168] ##STR00023##

[0169] A 10 mL flame dried and argonated schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (117 mg, 220 mol) and dissolved in a solution of (S)-(o,o,p-tri(n-heptyl)phenyl)BINOL (490 mg, 0.48 mmol 2.1 equiv. in 4 mL pyridine). The reaction was stirred for 19 h at r.t. followed by the addition of water (800 l, 44.4 mmol, 202 equiv.) and stirred additional 5 h at 80 C. until 31 P-NMR analysis shows clean hydrolysis to the desired product. After cooling to r.t. the reaction mixture was poured into 30 mL HCl.sub.(aq) and extracted with DCM (330 mL). The combined organic phases were dried over sodium sulfate, concentrated to dryness and purified by FCC (Biotage, gradient: hexanes up to hexanes/DCM (3:2)) to elute the desired product as a salt. Acidification was carried out by dissolving the salt in DCM (5 mL) and HCl.sub.(aq) (6M, 5 mL). The organic phase was isolated, concentrated to dryness followed by drying o.n. in h.v. to furnish the desired product as a colorless viscous oil (82%, 389 mg)

Example 12: Synthesis of (S,S)-4-(((2r)-4-oxido-2,6-bis(2,4,6-tri-(2-propyl)phenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(2,4,6-tri-(2-propyl)phenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine 4-oxide

[0170] ##STR00024##

[0171] A 25 mL flame dried and argonated schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (472 mg, 887 mol) and (S)-(o,o,p-tri(2-propyl)phenyl)BINOL (1.23 g, 1.78 mmol 2.0 equiv) followed by the addition of pyridine (9 mL). The reaction was stirred for 12 h at r.t. followed by the addition of water (320 l, 17.7 mmol, 20 equiv.) and stirred additional 16 h at 80 C. After cooling to r.t. the reaction mixture was poured into 20 mL HCl.sub.(aq) and extracted with DCM (330 mL). The combined organic phases were dried over sodium sulfate, concentrated to dryness and purified by FCC (Biotage, gradient: hexanes up to hexanes/DCM (3:2)) to elute the desired product as a salt. Acidification was carried out by dissolving the salt in DCM (10 mL) and HCl.sub.(aq) (6M, 10 mL). The organic phase was isolated, concentrated to dryness followed by drying o.n. in h.v. to furnish the desired product as a colorless solid (35%, 462 mg)

Example 13: Synthesis of 1,1,1-trifluoro-N-((2r)-4-(((2s)-4-oxido-2,6-bis(2,4,6-triisopropylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)imino)-2,6-bis(2,4,6-triisopropylphenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)methanesulfonamide

[0172] ##STR00025##

[0173] A flame dried 10 mL Young-schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (99.0 mg, 186 mol), (S)- 3,3-di(2,4,6-triisopropylphenyl)-[1,1-binaphthalene]-2,2-diol (268 mg, 388 mol 2.09 equiv.) followed by the addition of toluene (2 mL) and subsequent dropwise addition of NEt.sub.3 (109 L, 781 mol, 4.2 equiv.) to form a colorless suspension, which was stirred additional 1.5 h at r.t. TfNH.sub.2 (243 mg, 1.63 mmol, 8.76 equiv.) was added in one portion followed by addition of additional NEt.sub.3 (415 L, 2.98 mmol, 16.0 equiv.) and the suspension stirred additional 25 h at 80 C. 4-DMAP (20.5 mg, 0.167 mol, 0.90 equiv.) was added and the reaction mixture stirred 17 hat 110 C. Water (2 mL) and DCM (2 mL) was added and the emulsion stirred additional 16 h at r.t., followed by isolation of the organic phase, which was dried over sodium sulfate, concentrated to dryness and the resulting crude product was purified by FCC (hexanes/EtOAc 9:1) to elute the desired product as a salt. The salt was dissolved in DCM (10 mL) and acidified with HCl (6 M, 10 mL) for 30 min at r.t. The organic phase was isolated, concentrated to dryness and dried in high vacuum o.n. to afford the desired product in acidic form (64%, 194 mg, 186 mol).

Example 14: Synthesis of (S,S)-1,1,1-trifluoro-N-(4-((4-oxido-2,6-diphenyldinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)imino)-2,6-diphenyl-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)methanesulfonamide

[0174] ##STR00026##

[0175] A flame dried schlenk was charged with hexachlorobisphosphazonium hexachlorophosphate (62.8 mg, 118 mol), (S)-3,3-diphenyl-[1,1-binaphthalene]-2,2-diol (104 mg, 237 mol) followed by the addition of pyridine (1 mL). The yellow reaction mixture was stirred additional 3 h at r.t. followed by the addition of solid trifluoromethanesulfonamide (90 mg, 604 mol) and the resulting suspension was stirred for 72 h at r.t. Distilled water (100 l, 5.55 mmol) was added and the yellow suspension stirred for additional 4 h at r.t., followed by quenching with aqueous HCl (10%) and the aqueous phase was extracted with dichloromethane. The combined organic phase was dried over sodium sulfate, concentrated to dryness. The crude product was purified by flash column chromatography (hexanes/ethyl acetate/dichloromethane (4:2:4)) to furnish a colorless solid, which was filtered over a pad of Dowex 50WX80 (acidic form) to afford the desired product as a colorless solid (65 mg, 49%) which was reprecipitated from dichloromethane/pentane followed by drying in high vacuum.

Example 15: Synthesis of (S,S)-1,1,1-trifluoro-N-(4-((4-oxido-2,6-bis(4-(pentafluoro-l6-sulfanyl)phenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxa-phosphepin-4-yl)amino)-2,6-bis(4-(pentafluoro-l6-sulfanyl)phenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ylidene)methane-sulfonamide

[0176] ##STR00027##

[0177] A flame dried schlenk was charged with hexachlorobisphosphazonium hexachlorophosphate (56.8 g mg, 107 mol), (S)-3,3-bis(4-(pentafluoro-l6-sulfanyl)phenyl)-[1,1-binaphthalene]-2,2-diol (147 mg, 213 mol) followed by the addition of pyridine (1 mL). The yellow reaction mixture was stirred additional 3 h at r.t. followed by the addition of solid trifluoromethanesulfonamide (90 mg, 604 mol) and the resulting suspension was stirred for 17 h r.t. Distilled water (100 l, 5.55 mmol) was added and the yellow suspension stirred for additional 4 h at r.t., followed by quenching with aqueous HCl (10%) and the aqueous phase was extracted with dichloromethane. The combined organic phase was dried over sodium sulfate, concentrated to dryness. The crude product was purified by flash column chromatography (hexanes/ethyl acetate (5:1 to 3:1) to furnish a colorless solid, which was filtered over a pad of Dowex 50WX80 (acidic form) to afford the desired product as a colorless solid (123 mg, 71%) which was reprecipitated from dichloromethane/n-pentane followed by drying in high vacuum.

Example 16: Synthesis of N-(4-((4-oxido-2,6-bis(4-(trifluoromethyl)phenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(4-(trifluoromethyl)phenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxa-phosphepin-4-ylidene)-3,5-bis(trifluoromethyl)benzenesulfonamide

[0178] ##STR00028##

[0179] An under high vacuum flame-dried and argonated Schlenk flask was charged with HCPP (67.3 mg, 0.126 mmol, 1.0 equiv.), (S)-3,3-bis(4-trifluoromethylphenyl)-BINOL (161 mg, mmol, 2.0 equiv.) followed by the addition of pyridine (1 mL) to form a clear yellow solution, which was stirred until full consumption of BINOL (1 h) resulting in the formation of a suspension. 3,5-bis(trifluoromethyl)benzenesulfonamide (94.2 mg, 0.632 mmol, 4.9 equiv.) was added and the reaction mixture stirred additional 1 h at room temperature. Water (0.15 mL, 10 wt %) was added and the reaction stirred additional 16 h, at room temperature, followed by the addition of an excess of HCl (10 wt %) to quench the reaction. The aqueous phase was extracted with C.sub.2 Cl.sub.2 and the combined organic layers were washed with brine, dried over NaSO.sub.4 and concentrated to dryness. The obtained solid was purified by column chromatography (Pentane:Et.sub.2 O with a gradient of 4:1 to 2:1) to furnish the desired product as a salt which was further acidified as a DCM solution by filtration over a pad of DOWEX 50WX-8 to obtain the desired product in acidic form (65%, 51.3 mg, 94.0 mol)

Example 17: Synthesis of Sodium (S-phenyl-N-((trifluoromethyl) sulfonyl)sulfinimidoyl)-((trifluoromethyl)sulfonyl)amide

[0180] ##STR00029##

[0181] A 500 mL flame dried two necked flask with 100 mL dropping funnel was charged with potassium tert-butoxide (23.0 g, 205 mmol), tetrahydrofurane (250 mL) and cooled to 0 C. (ice bath). Iodine (46.1 g, 182 mmol) was added in small portions within 20 minutes under vigorous stirring of the resulting dark brown suspension. After full addition the resulting dark brown suspension was stirred additional 1 h at 0 C. The dropping funnel was charged with a solution of trifluoromethanesulfonamide (10.8 g, 72.6 mmol) and thiophenol (4.00 g, 36.3 mmol) in acetonitrile (50 mL). The solution of the dropping funnel was added dropwise within minutes to the dark brown suspension under vigorous stirring at 0 C. After full addition the resulting dark brown suspension was stirred additional 17 h at r.t. followed by the addition of a saturated aqueous solution of sodium thiosulfate until the dark brown suspension turned into a slightly yellow suspension. The suspension was transferred to a 1 L separating funnel. The 500 mL two necked round bottom flask was rinsed with diethylether (150 mL) and added to the dropping funnel. The organic phase was washed with sodium sulfate (twice, 200 mL each), brine (200 mL), dried over sodium sulfate and concentrated to dryness. After flash column chromatography (gradient, pure dichloromethane then dichloromethane/acetone (3:2)) the desired product was isolated as a colorless solid (8.54 g, 55%).

Example 18: Synthesis of N,N-(amino(phenyl)-16-sulfanediylidene)bis(1,1,1-trifluoromethane-sulfonamide)

[0182] ##STR00030##

[0183] A 20 mL microwave vessel was charged with sodium (S-phenyl-N-((trifluoromethyl)sulfonyl)sulfinimidoyl)-((trifluoromethyl)sulfonyl)amide (2.00 g, 4.69 mmol), Selectfluor (4.26 g, 12.0 mmol) and acetonitrile (10 mL). The suspension was heated for 60 minutes in a microwave (Biotage Initiator+) reactor (100 C., 1 bar overpressure) and was then transferred to a flame dried 100 mL round bottom flask with argon adapter. All volatile compounds were removed in high vacuum (1*10.sup.3 mbar) to afford a yellow precipitate. This precipitate was suspended in dichloromethane (20 mL) and transferred with argon overpressure through a PE-tube into a celite filled schlenk frit (3 cm height). The filtrate was collected in a 100 mL flame dried schlenk tube. The precipitate was washed two times with dichloromethane (20 mL each) and filtered and mentioned above. The combined dichloromethane solution containing the desired sulfonyl fluoride PhS(NTf).sub.2 F was treated with anhydrous ammonia gas for 15 minutes resulting in the formation of a colorless suspension. This suspension was transferred to a 250 mL round bottom flask and concentrated to dryness. Diethylether (50 mL) and aqueous HCl (6 M, 50 mL) were added and the emulsion transferred to a 250 mL separating funnel. The organic phase was washed additional two times with aqueous HCl (6 M, 50 mL each), brine and concentrated to dryness. The resulting colorless precipitate was recrystallized in toluene to afford the desired product as a colorless and crystalline solid (1.20 g, 61%).

Example 19: Synthesis of (S,S)- N,N-(((4-((4-oxido-2,6-diphenyldinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-diphenyl-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ylidene)amino)(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethanesulfonamide)

[0184] ##STR00031##

[0185] A 5 mL flame dried schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (146 mg, 274 mol), (S)-3,3-bis(phenyl)-[1,1-binaphthalene]-2,2-diol (239 mg, 546 mol) followed by the addition of pyridine (3 mL). The slightly yellow suspension was stirred for 3 h at r.t. followed by the addition of N,N-(amino(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethanesulfonamide) (345 mg, 823 mol) and was stirred 4 d at r.t. Distilled water (300 l mL, 16.6 mmol) was added resulting in a beige suspension which was stirred additional 16 h at r.t. The suspension was poured into a mixture of aqueous 6 M HCl (30 mL) and dichloromethane (30 mL) and was transferred to a separating funnel. The aqueous phase was extracted additional two times with dichloromethane (30 mL each) and the combined organic phase was dried over sodium sulfate and was concentrated to dryness. The crude product was further purified by flash column chromatography (ethyl acetate/hexanes (1:2)) to afford a colorless crystalline solid which was filtered through Dowex 50WX80 (acidic form, 8 cm height) to furnish the desired product as a colorless solid (100 mg, 26%).

Example 20: Synthesis of (S,S)-N,N-(((4-((2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4-oxidodinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ylidene)amino)(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethanesulfonamide)

[0186] ##STR00032##

[0187] A 25 mL flame dried schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (155 mg, 291 mol), (S)-3,3-bis(3,5-bis(trifluoromethyl)phenyl)-[1,1-binaphthalene]-2,2-diol followed by the addition of pyridine (5 mL). The slightly yellow suspension was stirred for 90 minutes at r.t. followed by the addition of N,N-(amino(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethanesulfonamide) (420 mg, 1 mmol) and was stirred 72 h at 60 C. After cooling to r.t. distilled water (1 mL, 27 mmol) was added resulting in a beige suspension which was stirred additional 24 h at r.t. The suspension was poured into a mixture of aqueous 6 M HCl (30 mL) and dichloromethane (30 mL) and was transferred to a separating funnel. The aqueous phase was extracted additional two times with dichloromethane (30 mL each) and the combined organic phase was dried over sodium sulfate and was concentrated to dryness. The crude product was further purified by flash column chromatography (ethyl acetate/hexanes (1:4)) to afford a colorless crystalline solid which was filtered through Dowex 50WX80 (acidic form, 8 cm height) to furnish the desired product as a colorless solid (92 mg, 16%).

Example 21: Synthesis of N-((2s)-4-(((E)-2-((Z)-but-2-en-1-ylidene)-4,8-dimesityl-6-((trifluoromethyl)sulfonamido)-1,2-dihydro-6l5-benzo[d]naphtha [1,2-f][1,3,2]dioxaphosphepin-6-ylidene)amino)-2,6-dimesityl-4l5-dinaphtho [2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ylidene)-1,1,1-trifluoromethane sulfonamide

[0188] ##STR00033##

[0189] A 10 mL flame dried schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (129 mg, 0.24 mmol, 1 equiv.), (S)-Mesityl-Binol (271 mg, 0.52 mmol, 2.1 equiv.) and suspended in toluene (5 mL). Triethylamine (0.15 mL, 1,09 mmol, 4.5 equiv.) was added dropwise via a Hamilton syringe under vigorous stirring forming a slightly orange suspension in which the color faded away within 5 minutes at r.t. The resulting colorless suspension was stirred additional 60 minutes at r.t. followed by addition of TfNH.sub.2 (289 mg, 1.94 mmol, 8 equiv.) additional triethylamine (0.54 mL, 3.88 mmol, 16 equiv.) was added and the suspension stirred additional 26 hours at 80 C. The orange suspension was cooled to r.t. followed by addition of 4-dimethylaminopyridine (26.6 mg, 0.22 mmol, 0.9 equiv.) and stirred for additional 6 d at 100 C. The reaction mixture was then analyzed by NMR (a small aliquote was transferred to an NMR tube under inert conditions, all volatiles removed in high vacuum followed by addition of DCM-d2) showing a conversion of approximately 60% to the desired product. The reaction mixture was then quenched with ca. 1 mL aqueous HCl (6 M) followed by dilution with dichloromethane (ca. 10 mL). The mixture was transferred to a 25 mL separation funnel and washed with HCl (6 M, 10 mL) followed by washing with sat. NaHCO.sub.3(aq) (2 times 10 mL each). The organic phase was dried over sodium sulfate, concentrated to dryness followed by FCC (Biotage, gradient: n-hexane/EtOAc (100/0) up to (60/40) to elute the intermediate, in which only one chloride has been substituted (36%, 114 mg) and the desired product as salt (m=126 mg, 44% yield referred to the sodium salt). 46 mg of this salt was dissolved in a small quantity of dichloromethane and passed through a column filled with Dowex 40Wx8 to obtain the desired product in acidic form (42 mg, 93%).

[0190] Example 22: 6,6-azanediylbis(7-methyl-7H-dibenzo[d,f][1,3,2]oxaza phosphepine 6-oxide

##STR00034##

[0191] A 10 mL flame dried schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (327 mg, 0.62 mmol, 1 equiv.), 2-(methylamino)-[1,1-biphenyl]-2-ol (245 mg, 1.25 mmol, 2 equiv.) and dissolved in precooled (0 C.) pyridine (3.50 mL). The yellow reaction mixture was stirred for 2.5 h at 0 C. (ice bath) followed by the addition of water (0.22 mL, 12.3 mmol, 20 equiv.). The reaction was then stirred o.n. at r.t. followed by the addition of 6 N HCl (ca. 5 mL) and extracting the aqueous phase with dichloromethane (320 mL). The combined organic phase was dried over sodium sulfate, concentrated to dryness followed by flash column chromatography (DCM/EtOAc (4/1)) to elute the desired product in salt form which was subsequently acidified with 6N HCl.sub.(aq)/DCM (10 mL 1/1 v/v/%). The desired product (153 mg, 49%) was isolated as a mixture of diastereomers, which were resolved by preparative HPLC (Deicel Chiralpak QN-AX, 150 mm, 21 mm, MeOH/HOAc, NH.sub.4Ac=98:2:0.5 (v/v/w), 20 mL/min) to afford the corresponding enantioenriched products.

Example 23: Synthesis of (S)-6-(((R)-6-oxido-7-tosyl-7H-dibenzo [d,f][1,3,2]oxazaphosphepin-6-yl)amino)-7-tosyl-7H-dibenzo[d,f][1,3,2] oxazaphosphepine 6-oxide

[0192] ##STR00035##

[0193] A 10 mL flame dried schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (35.4 mg, 72.0 mol, 1 equiv.), 2-(N-tosyl)-[1,1-biphenyl]-2-ol (54.5 mg, 152 mol, 2.1 equiv.) and dissolved in THF. NaH (dispersion, 60%, 8.69 mg, 217 mol, 3 equiv.) was added and the reaction stirred 1.5 h at r.t. Aqeuous NaOH (1 M, 700 l) was added and the reaction stirred additional 45 min at r.t. EtOAc (5 mL) was added and the organic phase washed with aqueous HCl (10%, 25 mL) and dried in vacuo to afford a crude product (52.1 mg). A part of this crude product was purified by preparative TLC (EtOAc/DCM 1:4) to afford the title product as salt, which comprises inherent chirality based on analytical HPLC measurement (150 mm Chiralpak QN-AX, 4.6 mm, MeOH/HOAc/NH.sub.4OAc=98.2:0.5 (v/v/w)).

Example 24: Synthesis of (S,S)-3,5-dibenzyl-4-(benzylamino)-N-(3,5-dibenzyl-4-(benzylamino)-4,5-dihydro-3H-4.SUP.5.-dinaphtho[2,1-d:1,2-f][1,3,2]diazaphosphepin-4-ylidene)-4,5-dihydro-3H-4.SUP.5.-dinaphtho[2,1-d:1,2-f][1,3,2]diazaphosphepin-4-iminium chloride

[0194] ##STR00036##

[0195] A flame dried schlenk was charged with hexachlorobisphosphazonium chloride (32.4 mg, 0.1 mmol), (S)-N2,N2-dibenzyl-(1,1-binaphthalene)-2,2-diamine (97.6 mg, 0.21 mmol) followed by the addition of pyridine (1 mL). The brown reaction mixture was stirred additional 12 h at 100 C. followed by the addition of distilled benzylamine (107.2 mg, 1 mmol). The resulting suspension was stirred additional 24 h at 110 C. followed by quenching with saturated ammonium chloride solution. The mixture was extracted with EtOAc, the combined organic phase dried over sodium sulfate and concentrated to dryness. The crude product was purified by flash column chromatography (dichloromethane/methanol) (100:1 to 50:1) to afford the desired product as a yellow solid (25%, 31.2 mg).

Example 25: Synthesis of (S,S)-4-(butylamino)-N-(4-(butylamino)-3,5-diphenyl-4,5-dihydro-3H-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]diazaphosphepin-4-ylidene)-3,5-diphenyl-4,5-dihydro-3H-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]diazaphosphepin-4-iminium chloride

[0196] ##STR00037##

[0197] A 10 mL flame dried schlenk was charged with hexachlorobisphosphazonium chloride (162 mg, 0.5 mmol, 1 equiv.), (S)-N2,N2-diphenyl-[1,1-binaphthalene]-2,2-diamine (436.2 mg, 1 mmol, 2 equiv.) followed by the addition of pyridine (1 mL). The brown reaction mixture was stirred additional 24 h at 120 C. followed by the addition of distilled n-Butylamine (365 mg, 5 mmol, 5 equiv.). The resulting suspension was stirred additional 24 h at 110 C. followed by quenching with saturated ammonium chloride solution. The mixture was extracted with EtOAc (320 mL), the combined organic phase dried over sodium sulfate and concentrated to dryness. The crude product was purified by flash column chromatography (dichloromethane/methanol) (100:1 to 50:1) to afford the desired product as a yellow solid (45%, 252 mg).

Example 26: Synthesis of (S,S)-3,5-di([1,1:3,1-terphenyl]-5-yl)-4-(butylamino)-N-(3,5-di([1,11:3,1-terphenyl]-5-yl)-4-(butylamino)-4,5-dihydro-3H-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]diazaphosphepin-4-ylidene)-4,5-dihydro-3H-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]diazaphosphepin-4-iminium chloride

[0198] ##STR00038##

[0199] A 10 mL flame dried schlenk was charged with hexachlorobisphosphazonium chloride (81 mg, 0.25 mmol, 1 equiv.), (S)-N2,N2-di([1,1:3,1-terphenyl]-5-yl)-[1,1-binaphthalene]-2,2-diamine (370 mg, 0.5 mmol, 2 equiv.) followed by the addition of pyridine (0.5 mL). The brown reaction mixture was stirred additional 24 h at 120 C. followed by the addition of distilled n-Butylamine (365 mg, 5 mmol, 10 equiv.). The resulting suspension was stirred additional 24 h at 110 C. followed by quenching with saturated ammonium chloride solution. The mixture was extracted with EtOAc (320 mL), the combined organic phase dried over sodium sulfate and concentrated to dryness. The crude product was purified by flash column chromatography (dichloromethane/methanol) (100:1 to 50:1) to afford the desired product as a yellow solid (54%, 233 mg).

Example 27: N,NY-((2s,2s)-azanediyIbis(2,6-bis(2,4,6-triethylphenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1,1,1-trifluoromethanesulfonamide)

[0200] ##STR00039##

[0201] A 10 mL flame-dried schlenk tube was charged with hexachlorobisphosphazonium hexachlorophosphate (45 mg, 0,085 mmol, 1.0 equiv.) and (S)-3,3-(o,o,p-tri(n-ethyl)phenyl)BINOL (110 mg, 0.18 mmol, 2.2 equiv.) and dissolved in toluene (1 mL). To the solution was added NEt.sub.3 (53 l, 0.38 mmol, 4.5 equiv.) dropwise under vigorous stirring. The resulting yellow suspension was stirred for 60 min at r.t. followed by the addition of H.sub.2NTf (100 mg, 0.68 mmol, 8 equiv.) and NEt.sub.3 (195 l, 137 mg, 1.35 mmol, 16,0 equiv.). The mixture was heated to 80 C. under stirring for 15 h and subsequently 4-DMAP (9.3 mg, mmol, 0.9 equiv.) was added at r.t. The reaction was stirred for 120 h at 120 C. The crude mixture was purified without work-up by FCC (Biotage, gradient: hexanes up to hexanes/EtOAc (5:1)) to elute the desired product as a salt. Acidification was carried out by dissolving the salt in Et.sub.2O (3 mL) and flushing the solution through a 5 cm pad of DOWEX 50WX8. The organic phase was concentrated to dryness furnish the desired product as a colorless solid (36%, 48 mg)

Example 28: N,N,N,N-(((azanediylbis(2,6-diphenyl-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxa-phosphepine-4-yl-4-ylidene))bis(azanylylidene))bis(phenyl-l6-sulfanyldiylidene))tetrakis(1,1,1-trifluoromethanesulfonamide)

[0202] ##STR00040##

[0203] A 25 mL flame dried schlenk flask was charged with hexachlorobisphosphazonium chloride (132 mg, 407 mol, 1 equiv.) and of N,N-(amino(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethane-sulfonamide) from example 18 (343 mg, 818 mol, 2 equiv.) and suspended in toluene (4 mL). The suspension was stirred for 15 minutes until gas development ceased. Sodium hydride (dispersion in mineral oil, 60%, 218 mg, 5.45 mmol, 13 equiv.) was added and the reaction mixture stirred 3 h at 60 C. (S)-3,3-(Phenyl)BINOL (401 mg, 914 mol, 2.2 equiv.) was added and the reaction mixture stirred for 23 h at 100 C. The reaction mixture was then carefully poured into sat. NaHCO.sub.3 and the aqueous layer extracted with DCM. The combined organic phases were washed with brine, dried over sodium sulfate and concentrated to dryness followed by purification by FCC (Biotage, gradient DCM up to DCM/MeOH (3:2)) to elute the desired product as a salt. This salt was then acidified by dissolving in a small quantitiy of DCM and flushing through a 5 cm pad of DOWEX 50WX8. The organic phase was concentrated to dryness to furnish the desired product in acidic form (60%, 437 mg).

Example 29: N,N-(azanediylbis(2,6-bis(4-(tert-butyl)phenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1,1,1-trifluoromethanesulfonamide)

[0204] ##STR00041##

[0205] A 10 mL flame dried schlenk flask was charged with hexachlorobisphosphazonium chloride (42 mg, 130 mol, 1 equiv.), TfNH.sub.2 (38.6 mg, 259 mol, 2 equiv.) and suspended in toluene (1 mL). The suspension was stirred for 1 h at r.t. followed by addition of sodium hydride (dispersion in mineral oil, 60%, 82.9 mg, 2.07 mmol, 16 equiv.) and stirred 6 h at 100 C. followed by addition of (S)-3,3-(4-tent-butylphenyl)BINOL (173 mg, 314 mol, 2.4 equiv.) and further stirred for 34 h at 100 C. The reaction mixture was then carefully poured into sat. NaHCO.sub.3 and the aqueous layer extracted with DCM. The combined organic phases were washed with brine, dried over sodium sulfate and concentrated to dryness followed by purification by FCC (Biotage, gradient DCM up to DCM/EtOAc(9:1)) to elute the desired product as a salt, which was acidified by dissolving in a small quantitiy of DCM and flushing through a 5 cm pad of DOWEX 50WX8. The organic phase was concentrated to dryness to furnish the desired product in acidic form (56%, 107 mg).

Example 30: Synthesis of (S,S)-N-(4-((2,6-bis(2-cyclohexyl-5-methylphenyl)-4-oxidodinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)amino)-2,6-bis(2-cyclohexyl-5-methylphenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-ylidene)-1,1,1-trifluoromethanesulfonamide

[0206] ##STR00042##

[0207] A 25 ml flame dried Schlenk-tube was charged with HCPP (265 mg, 498 mol, 1 equiv.), 3,3-bis(2-cyclohexyl-5-methylphenyl)-[1,1-binaphthalene]-2,2-diol (628 mg, 996 mol, 2 equiv.) followed by addition of pyridine (10 ml) to form a yellowish solution. The reaction was stirred 50 min at r.t., followed by addition of TfNH 2 (371 mg, 2.49 mmol (5 equiv.) and stirred 1 h at r.t. Water (1 ml, 55.5 mmol, 112 equiv.) was added and the resulting suspension stirred 6 h at r.t. The reaction mixture was poured into ice-cooled HCl.sub.(aq) (6 M, 100 ml), transferred to a separation funnel and the aqueous phase extracted with DCM (340 ml). The combined organic phase was dried over sodium sulfate, concentrated to dryness and the crude product purified by FCC (DCM/EtOAc 4:1) to elute the desired product as salt. The salt was dissolved in a small quantitiy of DCM (ca. 4 ml), overlayered with pentane and stand for 3 d in a freezer (20 C.) to form colorless crystals. The organic phase was decanted and the colorless crystals dissolved in 20 ml DCM followed by addition of HCl (6 M, 20 ml) and stirred for 30 min at r.t. The DCM phase was isolated, concentrated to dryness and further dried in h.v o.n. to afford the desired product in acidic form as a colorless solid (67%, 503 mg, 498 mol). [NMR analysis shows two sets of signals, which indicate the presence of rotamers (ratio 9:1).

Example 31: Synthesis of 1,1,1-trifluoro-N-((2s)-4-((4-oxido-2,6-bis(2,4,6-tripentylphenyl)dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)imino)-2,6-bis(2,4,6-tripentylphenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepin-4-yl)methanesulfonamide

[0208] ##STR00043##

[0209] A 10 ml round bottom flask with argon adapter was charged (S)-3,3-bis(2,4,6-tri-n-pentylphenyl)-BINOL (256 mg, 298 mol, 2 equiv.), HCPP (82 mg, 154 mol, 1 equiv.) followed by subsequent addition of toluene and Net3 (249 l, 1.79 mmol, 12 equiv.) to form a yellowish suspension which was stirred for 3 h at r.t. TfNH2 (177 mg, 1.19 mmol, 8 equiv.) was added and the reaction stirred for 23 hat r.t. followed by addition of H.sub.2O (268 l, 14.9 mmol, 100 equiv.), pyridine (1 ml, to increase the solubility and facilitate the hydrolysis) and stirred 3 h at 70 C. The reaction mixture was poured into aqueous HCl (6 M) and extracted with DCM. The combined organic DCM phase was concentrated to dryness and purified by FCC (Biotage, gradient: hexanes/DCM 100:0 up to 0:100; product elution with 60:40) to furnish the desired product as salt, which was acidified by dissolving in DCM (3 ml) and emulsion in HCl (6M, 3 ml). The emulsion was stirred for 30 min, the organic phase isolated, concentrated to dryness and dried o.n. in h.v. to afford the desired product in acidic form (79%, 231 mg, 149 mol).

Example 32: Synthesis of (S,S)-N,N-(azanediylbis(2,6-bis(2-(tert-butyl)spiro[cyclopentane-1,9-fluoren]-7-yl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(1,1,1-trifluoromethanesulfonamide)

[0210] ##STR00044##

[0211] ml flame-dried and argonated Schlenk tube was charged with HCPP (30 mg, 56 mol, 1.0 equiv.) and (S)-3,3-bis(2-(tert-butyl)spiro[cyclopentane-1,9-fluoren]-7-yl)-BINOL (64 mg, 116 mol, 2.05 equiv.) and dissolved in 0.8 ml toluene. To the solution was added NEt.sub.3 (35 l, 254 mol, 4.5 equiv.) dropwise under vigorous stirring. The resulting yellow suspension was stirred for 60 min at r.t. followed by the addition of H.sub.2 NTf (327 mg, 2.19 mmol, 8 equiv.). The mixture was heated to 120 C. under stirring for 36h. The crude mixture was purified without work-up by FCC (gradient: hexanes/EtOAc 1:0 to 9:1) to elute the desired product as a salt. Acidification was carried out by dissolving the salt in Et.sub.2 O (3 ml) and flushing the solution through a 5 cm pad of DOWEX 50WX2. The organic phase was concentrated to dryness to furnish the desired product as a colorless solid (70%, 392 mg)

Example 33: Synthesis of N,N,N,N-(((azanediylbis(2,6-diphenyl-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(azanylylidene))bis(phenyl-l6-sulfanyldiylidene))tetrakis(1,1,1-trifluoromethanesulfonamide)

[0212] ##STR00045##

[0213] A 25 ml flame dried and argonated schlenk flask was charged with hexachlorobisphosphazonium chloride (132 mg, 407 mol, 1 equiv.) and of N,N-(amino(phenyl)-l6-sulfanediylidene)bis(1,1,1-trifluoromethane-sulfonamide) from example 18 (343 mg, 818 mol, 2 equiv.) and suspended in toluene (4 ml). The suspension was stirred for 15 minutes until gas development ceased. Sodium hydride (dispersion in mineral oil, 60%, 218 mg, 5.45 mmol, 13 equiv.) was added and the reaction mixture stirred 3 h at 60 C. (S)-3,3-(Phenyl)BINOL (401 mg, 914 mol, 2.2 equiv.) was added and the reaction mixture stirred for 23 h at 100 C. The reaction mixture was then carefully poured into sat. NaHCO.sub.3 and the aqueous layer extracted with DCM. The combined organic phases were washed with brine, dried over sodium sulfate and concentrated to dryness followed by purification by FCC (Biotage, gradient DCM up to DCM/MeOH (3:2)) to elute the desired product as a salt. This salt was then acidified by dissolving in a small quantitiy of DCM and flushing through a 5 cm pad of DOWEX 50WX8. The organic phase was concentrated to dryness to furnish the desired product in acidic form (60%, 437 mg).

Example 34: Synthesis of N,N,N,N-(((azanediylbis(2,6-bis(3,5-bis(trifluoromethyl)phenyl)-4l5-dinaphtho[2,1-d:1,2-f][1,3,2]dioxaphosphepine-4-yl-4-ylidene))bis(azanylylidene))bis(phenyl-l6-sulfanyldiylidene))tetrakis(1,1,1-trifluoromethanesulfonamide)

[0214] ##STR00046##

[0215] A 10 ml schlenk-tube was charged with HCPC (73.0 mg, 0.23 mmol), phenylbis(trifluoromethylsulfonylimino)sulfon-amide (191 mg, 0.46 mmol, 2 equiv.) and suspended in 2 ml toluene. The reaction was stirred 30 min at r.t. (150 rpm) until the gas development ceased. Sodium hydride (dispersion in mineral oil, 60%; 116 mg, 2.90 mmol, 13 equiv.) was added and the resulting suspension stirred for 2 h in a pre-heated metal block to 110 C. (S,S)-3,3-(m,m-bistrifluoromethylphenyl)BINOL was added in one portion and the sealed schlenk-flask and 44 h stirred at 110 C. The reaction mixture was cooled to r.t., diluted with DCM and poured into sat. NaHCO3(aq). The aqueous phase was extracted with DCM (420 ml), the combined organic phase dried over sodium sulfate and concentrated to dryness. Flash column purification (Biotage gradient; DCM/MeOH up to 4/1) yields the desired product as a salt, which was acidified by dissolving the product in a small quantitiy of DCM and passing through pre-activated Dowex40WX8 to afford the desired product in acidic form (81%, 426 mg, 0.18 mmol).

CONCLUSION

[0216] In summary, the inventors have developed a new methodology, allowing a rapid and highly efficient single-flask synthesis of a broad range of dimeric phosphazene derived catalysts utilizing hexachlorobisphosphazonium salts as a building block. Novel IDPs, iIDPs and IDPis with unique structural confinement are accessible in a straightforward and operationally simple synthesis and can be used for asymmetric catalysis

[0217] With a new access of novel and unexplored dimeric phosphazene catalysts with unique structurally confined cavities, the inventors started to focus their attention to small substrates, specifically those, which so far remained elusive to stereoselectively control in asymmetric catalysis. Propyl methyl sulfide, a substrate, which contains two structurally very similar groups, has so far, not been catalytically oxidized with excellent enantioselectivities.

[0218] Surprisingly, the new accessibility of new extremely confined IDP's resulted in a rapid identification of IDP from Example 9 for the asymmetric sulfoxidation (J. Am. Chem. Soc. 2012, 134, 10765) of this particular challenging substrate with an enantiomeric ratio of 95:5. Excellent enantioselectivities of propyl methyl sulfoxide illustrate the importance and impact of this new catalyst synthesis methodology to design new, previously not accessible catalysts with high confinement, solving tremendous challenges in asymmetric catalysis. The utility of those new catalysts are currently being investigated in our laboratory.

[0219] The inventors anticipate, that the utilization of hexachlorobisphosphazonium salts and derivatives thereof as a building block towards the synthesis of imidodiphosphoryl compounds might find future application towards the synthesis of novel, structurally distinct catalyst motifs, which might find application in the field of Brnsted acid and Brnsted base as well as Lewis acid and Lewis base catalysis.