Chiral diphenyldiphosphines and d-8 metal complexes thereof

Abstract

Compounds of formula III, wherein R 6 und R 7 signify identical or different secondary phosphino; R 8 is —CH 2 —OH, —CH 2 —NH 2 , —CH 2 —O—B—FU, —CH 2 —NH 2 —B—FU, or —O—B—FU; R 9 has the same significance as R 8 or is C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy; or R 8 and R 9 together signify HOCH(CH 2 —O—) 2 , H 2 NCH—(CH 2 —O—) 2 , FU—B—OCH(CH 2 —O—) 2 or FU—B—HNCH(CH 2 —O—) 2 ; B is a bridging group; and FU is a functional group. The compounds may be bonded to inorganic or organic carriers. Their d-8 metal complexes are valuable catalysts for the enantioselective hydrogenation of prochiral organic compounds with carbon multiple bonds or carbon/hetero atom multiple bonds.

What is claimed is:  
     
         1 . Compounds of formula 1,  
       
         
           
           
               
               
           
         
       
       wherein 
 R 1  is methyl chloride, methyl bromide or methyl iodide, R 2  is C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy or has the same significance as R 1 , and R 3  is Br, I or —NH 2 .  
 
     
     
         2 . Compounds of formula II,  
       
         
           
           
               
               
           
         
       
       wherein 
 R 3  is Br, I or —NH 2 ,  
 R 4  is hydroxymethyl, aminomethyl, hydroxy-, amino- or cyano-C 2 -C 8 -alkoxy, hydroxy-, amino- or cyano-C 2 -C 8 -alkoxymethyl, or hydroxy-, amino- or cyano-C 2 -C 8 -alkylaminomethyl, and R 5  has the same significance as R 4 , or R 5  is C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, or  
 R 4  and R 5  together are HOCH(CH 2 —O—) 2 , H 2 NCH(CH 2 —O—) 2 , or hydroxy-, amino- or cyano-C 2 -C 8 -alkylOCH(CH 2 —O—) 2 .  
 
     
     
         3 . Compounds of formula III,  
       
         
           
           
               
               
           
         
       
       wherein 
 R 6  and R 7  signify identical or different secondary phosphino,  
 R 8  is —CH 2 —OH, —CH 2 —NH 2 , —CH 2 —O—B—(FU) p , —CH 2 —NR′—B—(FU) p , or —O—B—(FU) p ,  
 R 9  has the same significance as R 8  or is C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, or  
 R 8  and R 9  together signify HOCH(CH 2 —O—) 2 , H 2 NCH(CH 2 —O—) 2 , (FU) p —B—OCH(CH 2 —O—) 2  or (FU) p —B—R′NCH(CH 2 —O—) 2 ,  
 R is H or C 1 -C 4  alkyl;  
 B is a bridging group,  
 FU is a functional group,  
 p is a number from 1 to 6, and  
 NH 2  groups are present as such or as masked isocyanate groups.  
 
     
     
         4 . Compounds according to  claim 3 , in which the secondary phosphino group corresponds to formula —PR 10 R 11 , wherein R 10  and R 11 , independently of one another, are C 1 -C 12 -alkyl, C 5 -C 12 -cycloalkyl, phenyl, C 5 -C 12 -cycloalkyl substituted by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy, or phenyl mono- to trisubstituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, —SiR 12 R 13 R 14 , halogen, —SO 3 M, —CO 2 M, —PO 3 M, —NR 15 R 16 , —[ + NR 15 R 16 R 17 ]X −  or C 1 -C 5 -fluoroalkyl; R 10  and R 11  together are tetra- or pentamethylene either unsubstituted or mono- to trisubstituted by C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, —SiR 12 R 13 R 14 , halogen, —SO 3 M, —CO 2 M, —PO 3 M, —NR 15 R 16 , —[ + NR 15 R 16 R 17 ]X −  or C 1 -C 5 -fluoroalkyl, or the group —PR 10 R 11  represents a radical of formulae  
       
         
           
           
               
               
           
         
         and R 12 , R 13  and R 14  independently of one another, are C 1 -C 12 -alkyl or phenyl  
         R 15  and R 16 , independently of one another, are H, C 1 -C 12 -alkyl or phenyl, or R 15  and R 16  together are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene;  
         R 17  is H or C 1 -C 4 -alkyl;  
         M is H or an alkali metal;  
         X is the anion of a monobasic acid;  
         halogen is fluorine, chlorine, bromine or iodine.  
       
     
     
         5 . Metal complexes of formulae V, Va and Vb of d-8 metals with the compounds of formula III,  
       
         
           
           
               
               
           
         
         whereby R 6 , R 7 , R 8  and R 9  have the above-mentioned significances and preferences;  
         Y denotes two monoolefin ligands or one diene ligand;  
         Me signifies a d-8 metal selected from the group Ir and Rh;  
         D is —Cl, —Br or —I; and  
         E is the anion of an oxyacid or complex acid;  
         X 2  and X 2 ′ are identical or different and have the significance of D or E, or X 2  and X 2 ′ are allyl or 2-methylallyl, or X 2  has the significance of D and E and X 2 ′ is hydride.  
       
     
     
         6 . Solid inorganic carrier, which has diphosphine ligands of formula IIIa that are bonded at the surface by one or two silyl groups of the radical of formula  
       
         
           
           
               
               
           
         
         wherein the group B—FU in radicals R 8  and R 9  is a radical of formula  
         —X 3 —C(O)—NH—R 27 —Si(R 25 ) n (R 26 O) 3-n    
         wherein X 3  signifies —O—, —NH— or NH(C 1 -C 4 -alkyl), R 27  is C 1 -C 12 -alkylene, R 26  is C 1 -C 12  alkyl, R 25  is C 1 -C 4 -alkyl or OR 26  and n is 0, 1 or 2.  
       
     
     
         7 . Inorganic or organic polymeric carriers, to which diphosphines of formula III  
       
         
           
           
               
               
           
         
       
       are bonded, which are characterised in that they are bonded to the inorganic or polymeric organic carrier by the functional group FU, whereby the radicals FU, R 6 , R 7 , R 8  and R 9  have the significances given in  claim 3 .  
     
     
         8 . d-8 metal complexes of inorganic or organic polymeric carriers, to which diphenyidiphosphines of formula VII, VIIa or VIIb  
       
         
           
           
               
               
           
         
       
       are bonded by at least one HO—, H 2 N— group or functional group FU, whereby the radicals R 6 , R 7 , R 8 , R 9 , Me, E, Y, X 2  and X 2 ′ and the carrier have the significances given in  claim 5 .  
     
     
         9 . Diphenyidiphosphine ligands of formula III according to  claim 3  and their d-8 metal complexes of formulae V, Va and Vb according to  claim 5 , which contain solubility-enhancing or adsorption-facilitating groups bonded to at least one HO—, H 2 N— or functional group FU, and which have a molecular weight of less than 5000 daltons, and which can be separated by extraction with immiscible liquids or by adsorption on a carrier.  
     
     
         10 . Process for the asymmetric hydrogenation of compounds with carbon double bonds or carbon/hetero atom double bonds, whereby the compounds are reacted with hydrogen at a temperature of −20 to 80° C. and at a hydrogen pressure of 10 5  to 2×10 7  Pa in the presence of catalytic amounts of d-8 metal complexes according to claims  5 ,  8  or  9 .