Process for preparing dimeric phosphazene derived BrØnsted acids

1 . Process for preparing a chiral imidodiphosphoryl compound of formula (I) or a tautomeric or ionic form thereof:

wherein in formula (I):

X is the same or different on each P and represents O, S, Se, CR C 2 or NR C ,

Z 1 to Z 4 are, independently from each other, the same or different and each represents O, S, Se or NR 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 I R II R III or a substituted silicon-SiR I R II R III , wherein R I , R II and R III may be same or different and each stands for hydrogen, halogen, an optionally —O— bonded C 1 to C 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 5 to C 18 heteroaromatic hydrocarbon, a C 6 to C 18 aromatic hydrocarbon or partially arene-hydrogenated forms thereof, each hydrocarbon optionally being substituted by one or more groups selected from C 1 to C 20 straight chain, branched chain or cyclic aliphatic hydrocarbons, or one or more heterosubstituents,

R 1 , R 2 , R 3 and R 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 1 may form a bond with any one of R 2 , R 3 or R 4 and the other two of R 2 , R 3 or R 4 may form a bond with each other, or whereby any of R 1 , R 2 , R 3 , R 4 , X 1 and X 2 may form a bond with each other, when R 1 , R 2 , R 3 and R 4 each represent an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, heteroaromatic hydrocarbon group;

R C represents, independently from each other, an aliphatic hydrocarbon group, heteroaliphatic hydrocarbon group, aromatic hydrocarbon group, an heteroaromatic hydrocarbon group, or R N ;

with the proviso that at least one of R 1 , R 2 , R 3 , R 4 or R 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 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 1 to C 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 C , amino —NH 2 , or substituted amino —NHR C , —NR C 2 wherein R 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 6 to C 18 aromatic hydrocarbon, optionally having at least one substituent selected from halogen, a C 1 to C 6 aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino ═NH, substituted imino ═NR C , amino —NH 2 or substituted amino —NHR C , —NR C 2 wherein R 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, —(P═O)-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 2 to C 18 heteroaromatic hydrocarbon, optionally having at least one substituent selected from halogen, a C 1 to C 6 aliphatic hydrocarbon, optionally having at least one substituent selected from halogen, cyano, nitro, imino ═NH, substituted imino ═NR C , amino-NH 2 , or substituted amino-NHR C , NR C 2 wherein R 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 C═O, S═O or P═O moiety, ═O may be replaced by an imino group ═N—R′, and/or for those groups of i.), ii.) and iii.), having at least one C—OR, S—OR or P—OR moiety, —OR may be replaced by an amino group-NR′R″, 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 3 P═N + ═PQ 3 A −   (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 − 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 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 W W 2 , wherein X W has the meaning of any of O, S, Se, CR C 2 , or NR C , wherein R C and W have the meanings as defined above,

wherein up to four nucleophilic groups Z 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 C Z W n W, wherein R C has the meaning as defined above, Z W is the same or different on each compound and has the meaning of any of Z 1 to Z 4 ; and W and n have the meanings as defined above,

wherein at least one nucleophilic group X W being present on one to two optionally chiral bivalent compounds of formula (III) X W W 2 , wherein X W has the meaning of any of CR C 2 or NR C ; wherein R C has the meaning as defined above, or at least one nucleophilic groups Z W being present on one to four optionally chiral monovalent compounds of formula (IV) R C Z W n W, wherein R C has the meaning as defined above; Z 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 1 to R 4 is chiral, or at least two of R 1 to R 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 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 W W 2 or two nucleophilic groups X 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 W W 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 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 C Z W n W, wherein R C has the meaning as defined in claim 1 , Z W is the same or different and has the meaning of any of Z 1 to Z 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 1 to Z 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 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 C Z W n W, wherein R C has the meaning as defined in claim 1 , Z W is the same or different and has the meaning of any of Z 1 to Z 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 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 W W 2 or two nucleophilic groups X 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 W W 2 , respectively, are reacted with the reaction product of the first reaction step, and, when in the second step, one nucleophilic group X W present on one optionally chiral compound of formula (III) X W W 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 1 to Z 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 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 C Z W n W, wherein R C has the meaning as defined in claim 1 , Z W is the same or different and has the meaning of any of Z 1 to Z 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 1 to Z 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 W on the compound of formula (III) X W W 2 , wherein W has the meaning as defined in claim 1 , which are CR C 2 or NR C and four nucleophilic groups Z W on the compound of formula (IV) R C Z W n W, wherein R C has the meaning as defined in claim 1 , Z W is the same or different and has the meaning of any of Z 1 to Z 4 , W has the meaning as defined in claim 1 and n is 0 or 1, are present on one optionally chiral compound and are stepwise reacted with the bisphosphazene compound of formula (II), wherein Z 1 to Z 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 W , which can be the same or different from each other and which are present on two optionally chiral compounds of formula (IV) R C Z W n W, wherein R C has the meaning as defined in claim 1 , Z W is the same or different and has the meaning of any of Z 1 to Z 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 3 P═N + ═PQ 3 A −   (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 represents a halogenide or weakly coordinating anion,

wherein said two optionally chiral compounds of formula (IV) R C Z W n W, which may be the same or different, are each represented by a structural unit of formula (V):

wherein Z 1 , Z 2 , Z 3 , Z 4 , R 1 , R 2 , R 3 , and R 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 1,3 —R 1,3 —R 2,4 —Z 2,4 , 1,1′binaphthyl, 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 2 to alkyl C 18 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 1 to C 20 aliphatic hydrocarbon, optionally having one or more unsaturated bonds, a C 6 to C 18 aromatic hydrocarbon or a C 5 to C 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 W W 2 , which may be the same or different, are represented by R N —NH 2 , wherein R 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):

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 1 to C 20 aliphatic hydrocarbon, optionally having one or more unsaturated bonds, a C 6 to C 18 aromatic hydrocarbon or a C 5 to C 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 W and W are as defined in claim 1 .

10 . 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 Brønsted acid/Brønsted 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).