Chiral ligands for application in asymmetric syntheses

1. A compound of the formula (I)

in which B is a bivalent moiety of the formula —(CHR 1 ) n —(R 2 C═CR 3 )—(CHR 4 ) m where R 1 , R 2 , R 3 and R 4 are each independently hydrogen or alkyl, and n and m are each independently zero or an integer from 1 to 8, where, however, the sum of n and m is from 1 to 8, and in which, moreover,

G is chlorine or hydrogen and

R′ and R″ are each independently aryl or alkyl or

in which B is a bivalent moiety of the formula —(CHR 1 ) n —(CR 2 R 3 ) m —(CHR 4 ) o where R 1 , R 2 , R 3 and R 4 are each independently hydrogen or alkyl, and n, m and o are each independently zero or an integer from 1 to 8, where the sum of n, m and o is from 1 to 8, G is chlorine and

R′ and R″ are each independently aryl or alkyl.

2. The compound as claimed in claim 1 , characterized in that R 1 , R 2 , R 3 and R 4 are each independently hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl and n-pentyl.

3. The compound as claimed in claim 1 , characterized in that R′ and R″ are each independently C 3 -C 8 -alkyl or C 5 -C 10 -aryl which may be unsubstituted, monosubstituted or polysubstituted by radicals which are selected from the group of chlorine, fluorine, cyano, phenyl, C 1 -C 6 -alkoxy and C 1 -C 6 -alkyl.

4. The compound as claimed in claim 1 , characterized in that they are the following:

(R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(diphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(dicyclohexyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butyl-4-methoxyphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethylphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethyl-4-methoxyphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-4-fluorophenyl)phosphine and also (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butylphenyl)phosphine and also the corresponding trans compounds, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(diphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(dicyclohexyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butyl-4-methoxyphenyl)-phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethylphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethyl-4-methoxyphenyl)phosphine, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-4-fluorophenyl)phosphine and also (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butylphenyl)phosphine, the stereoisomeric (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-butanedioxy)biphenyl-2,2′-diyl]-bis(diphenylphosphines], the stereoisomeric (R) and (S)-[5,5′-dichloro-6,6′-(1,3-butanedioxy)biphenyl-2,2′-diyl]bis(diphenylphosphines) and also any mixtures of the enantiomers.

5. A process for preparing compounds of the formula (IV)

in which B, G, R′ and R″ are each as defined in claim 1 , characterized in that compounds of the formula (III)

are reacted with a compound of the formula (VIa) or (VIb) or successively with two different compounds of the formulae (VIa) and (VIb)

X 3 —(CHR 1 ) n —R 2 C═CHR 5   (VIa)

X 4 —(CHR 4 ) m —R 3 C═CHR 6   (VIb)

in which X 3 and X 4 are each chlorine, bromine, iodine or a sulfonate and

R 1 , R 2 , R 3 , R 4 , m, and n, are each as defined in claim 1 , and R 5 and R 6 are each independently hydrogen or C 1 -C 4 -alkyl

to give compounds of the formula (VII)

and the compounds of the formula (VII) are then converted in the presence of an olefin metathesis catalyst to compounds of the formula (IV).

6. The process as claimed in claim 5 , characterized in that the compounds of the formula (VII) are subsequently reduced to compounds of the formula (I) as claimed in claim 1 .

7. The compound of the formula (VII)

in which G, R 1 , R 2 , R 3 , R 4 , R′, R″, n, and m are each as defined in claim 1 and R 5 and R 6 are each independently hydrogen or C 1 -C 4 -alkyl.

8. The compound as claimed in claim 7 , characterized in that they are the following:

(R)- and (S)-[5,5′-dichloro-6,6′-(bisallyloxy)biphenyl-2,2′-diyl]bis[(di-cyclohexyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(bisallyloxy)-biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butyl-4-methoxyphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(bisallyloxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethylphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(bisallyloxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethyl-4-methoxyphenyl)-phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(bisallyloxy)biphenyl-2,2′-diyl]bis[(di-4-fluorophenyl)phosphine oxide and also (R)- and (S)-[5,5′-dichloro-6,6′-(bisallyloxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butylphenyl)phosphine oxide.

9. A compound of the formula (IV)

in which B, R′ and R″ are each as defined in claim 1 .

10. The compound as claimed in claim 9 , characterized in that they are the following:

(R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(dicyclohexyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butyl-4-methoxy-phenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethylphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethyl-4-methoxyphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-4-fluorophenyl)phosphine oxide and also (R)- and (S)-[5,5′-dichloro-6,6′-(cis-1,4-but-2-enedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert.-butylphenyl)phosphine oxide and also the corresponding trans compounds and also (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-cyclohexyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butyl-4-methoxyphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethylphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-dimethyl-4-methoxyphenyl)phosphine oxide, (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-4-fluorophenyl)phosphine oxide and also (R)- and (S)-[5,5′-dichloro-6,6′-(1,3-propanedioxy)biphenyl-2,2′-diyl]bis[(di-3,5-di-tert-butylphenyl)phosphine oxide, the stereoisomeric (R)-[5,5′-dichloro-6,6′-(1,3-butanedioxy)biphenyl-2,2′-diyl]-bis(diphenylphosphine oxides), the stereoisomeric (S)-[5,5′-dichloro-6,6′-(1,3-butanedioxy)biphenyl-2,2′-diyl]bis(diphenylphosphine oxides) and also any mixtures of the enantiomers.

11. A transition metal complex comprising compounds according to claim 1 .

12. A catalyst comprising transition metal complex as claimed in claim 11 .

13. A process for the asymmetrical hydrogenation of prochiral C═C bonds, C═O bonds, or C═N bonds comprising hydrogenating the prochiral C═C bonds, C═O bonds, or C═N bonds in the presence of a catalyst according to claim 12 .