Chiral ligands for application in asymmetric syntheses

Abstract

The present invention relates to biarylbisphosphines and intermediates thereof. The scope of the invention further encompasses catalysts preparable from the biarylbisphosphines and their use in asymmetric syntheses.

1 . Compounds 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, preferably C 1 -C 6 -alkyl, and n, m and o are each independently zero or an integer from 1 to 8, where, however, the sum of n, m and o is from 1 to 8, preferably 3 or 4, and in which, moreover, G is chlorine and  
       R′ and R″ are each independently aryl or alkyl  
     
   
   
       2 . Compounds 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 . Compounds as claimed in at least one of claims  1  and  2 , 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 . Compounds as claimed in at least one of  claims 1  to  3 , 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  and R 4  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 . Compounds of the formula (VII)  
     
       
         
         
             
             
         
       
       in which R 1 , R 2 , R 3 , R 4 , R′ and R″ are each as defined in  claim 1  and  
       R 5  and R 6  are each independently hydrogen or C 1 -C 4 -alkyl.  
     
   
   
       8 . Compounds 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 . Compounds of the formula (IV)  
     
       
         
         
             
             
         
       
       in which B, R′ and R″ are each as defined in  claim 1 .  
     
   
   
       10 . Compounds 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-methoxyphenyl)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 . Transition metal complexes comprising compounds as claimed in one or more of  claims 1  to  4 .  
   
   
       12 . Catalysts comprising transition metal complexes as claimed in  claim 11 .  
   
   
       13 . A process for the transition metal-catalyzed preparation of enantiomerically enriched compounds, characterized in that it is carried out in the presence of catalysts as claimed in  claim 13.