Ferrocenyl diphosphines as ligands for homogeneous catalysts

Abstract

Compounds of formula Iwherein R1 is C1-C8alkyl, phenyl or phenyl which is substituted by 1 to 3 C1-C4alkyl or C1-C4alkoxy groups; R2 and R3 are identical and are C1-C12alkyl, C5-C12cycloalkyl or C1-C4alkyl- or C1-C4alkoxy-substituted C5-C12cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, -SiR4R5R6, halogen, -SO3M, -CO2M, -PO3M, -NR7R8 and -[⊕NR7R8R9]X⊖; or R2 and R3 are different and are C1-C12alkyl, C5-C12cycloalkyl, C1-C4alkyl- or C1-C4-alkoxy-substituted C5-C12cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C1-C4alkyl, C1-C4alkoxy, -SiR4R5R6, halogen, -SO3M, -CO2M, -PO3M2, -NR7R8 and -[⊕NR7R8R9]X⊖; or the group -PR2R3 is a radical of formula IIand R4, R5 and R6 are each independently of one another C1-C12alkyl or phenyl, R7 and R8 are H, C1-C2alkyl, phenyl or R7 and R8, taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R9 is H or C1-C4alkyl, M is H or an alkali metal, X⊖ is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of their racemates and diastereomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds, containing carbon double bonds or carbon/hetero atom double bonds.

What is claimed is:  
     
       1. A compound of formula I                    
       wherein R 1  is C 1 -C 8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups; R 2  and R 3  are identical and are C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl or C 1 -C 4 alkyl- or C 1 -C 4 alkoxy-substituted C 5 -C 12 cycloalkyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, —SiR 4 R 5 R 6 , halogen, —SO 3 M, —CO 2 M, —PO 3 M, —NR 7 R 8  and —[⊕NR 7 R 8 R 9 ]X⊖; or R 2  and R 3  are different and are C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl- or C 4 alkoxy-substituted C 5 -C 12  cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkoxy, —SiR 4 R 5 R 6 , halogen, —SO 3 M, —CO 2 M, —PO 3 M 2 , —NR 7 R 8  and —[⊕NR 7 R 8 R 9 ]X⊖; or the group —PR 2 R 3  is a radical of formula II                    
       and R 4 , R 5  and R 6  are each independently of one another C 1 -C 12 alkyl or phenyl, R 7  and R 8  are H, C 1 -C 12 alkyl, phenyl, or R 7  and R 8 , taken together, are tetramethylene, pentamethylene or 3-oxa-1,5-pentylene, R 9  is H or C 1 -C 4 alkyl, M is H or an alkali metal, X⊖ is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of the racemate or diastereoisomer or mixture of diastereoisomers. 
     
     
       2. A compound of formula I according to claim  1   16 , wherein R 1  is C 1 -C 4 alkyl. 
     
     
       3. A compound of formula I according to claim  2 , wherein R 1  is methyl or ethyl. 
     
     
       4. A compound of formula I according to claim  1   16 , wherein R 1  is phenyl or phenyl which is substituted by 1 or 2 C 1 -C 4 alkyl or C 1 -C 4 alkoxy groups. 
     
     
       5. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  are C 1 -C 8 alkyl. 
     
     
       6. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  are identical and are isopropyl or tert-butyl. 
     
     
       7. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  as cycloalkyl contain 5 to 8 ring carbon atoms. 
     
     
       8. A compound of formula I according to claim  7  wherein R 2  and R 3  as cycloalkyl are cyctopentyl or cyclohexyl. 
     
     
       9. A compound of formula I according to claim  1 , wherein R 2  and R 3  as substituted phenyl are selected from the group consisting of 2-methylphen-1-yl, 3-methylphen-1-yl, 4-methylphen-1-yl, 2- or 4-ethylphen-1-yl, 2- or 4-isopropylphen-1-yl, 2- or 4-tert-butylphen-1-yl, 2-methoxyphen-1-yl, 3-methoxyphen-1-yl, 4-methoxyphen-1-yl, 2- or 4-ethoxyphen-1-yl, 4-trimethylsilyphen-1-yl, 2- or 4-fluorophen-1-yl, 2,4-difluorophen-1-yl, 2- or 4-chlorophen-1-yl, 2,4-dichlorophen-1-yl, 2,4-dimethylphen-1-yl, 3,5-dimethylphen-1-yl, 2-methoxy-4-methylphen-1-yl, 3,5-dimethyl-4-methoxyphen-1-yl, 3,5-dimethyl-4-(dimethylamino)-phen-1-yl, 2- or 4-aminophen-1-yl, 2- or 4-methylaminophen-1-yl, 2- or 4-(dimethylamino)phen 1-yl, 2- or 4-SO 3 H-phen-1-yl, 2- or 4-SO 3 Na-phen-1-yl, 2- or 4-[⊕NH 3 Cl⊖]phen-1-yl, 3,4,5-trimethylphen-1-yl and 2,4,6-trimethylphen-1-yl. 
     
     
       10. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  are identical substituents selected from the group consisting of cyclohexyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1-yl-, 2- or 4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl and 3,5 dimethyl-4-methoxyphen-1-yl. 
     
     
       11. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  are different and R 2  is phenyl and R 3  is selected from the group consisting of cyclohexyl, 2- or 4-methylphen-1-yl, 2- or 4-methoxyphen-1-yl, 3,5-dimethyl-4-(dimethylamino)phen-1-yl, 3,5-dimethyl-4-methoxyphen-1-yl and 4-tert-butyl-phen-1-yl. 
     
     
       12. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  are identical substituents and are cyclohexyl. 
     
     
       13. A compound of formula I according to claim  1   16 , wherein R 2  and R 3  are identical substituents and are tert-butyl or o-anisyl. 
     
     
       14. A compound of formula I according to claim  1   16 , wherein R 2  is phenyl and R 3  is o-anisyl. 
     
     
       15. A compound of formula I according claim  1 , wherein R 1  is methyl and R 2  and R 3  are each cyclohexyl. 
     
     
       16. A compound of formula I                    
         wherein R   1    is C   1   -C   8   alkyl, phenyl or phenyl which is substituted by  1  to  3  C   1   -C   4   alkyl or C   1   -C   4   alkoxy groups; R   3    and R   3    are identical and are C   1   -C   12   alkyl, C   5   -C   12   cycloalkyl or C   1   -C   4   alkyl -  or C   1   -C   4   alkoxy - substituted C   5   -C   12   cycloalkyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C   1   -C   4   alkyl, C   1   -C   4   alkoxy, —SiR   4   R   5   R   6   , halogen, —SO   3   M, —CO   2   M, —PO   3   M, —NR   7   R   8    and —[⊕NR   7   R   8   R   9   ]X⊖; or R   2    and R   3    are different and are C   1   -C   12   alkyl, C   5   -C   12   cycloalkyl, C   1   -C   4   alkyl -  or C   1   -C   4   alkoxy - substituted C   5   -C   12   cycloalkyl, phenyl or phenyl which is substituted by one to three identical or different members selected from the group consisting of C   1   -C   4   alkyl, C   1   -C   4   alkoxy, —SiR   4   R   5   R   6   , halogen, —SO   3   M, —CO   2   M, —PO   3   M   2   , —NR   7   R   8    and —[⊕NR   7   R   8   R   9   ]X⊖; or a group —PR   2   R   3    is a radical of formula II                      
         and R   4   , R   5    and R   6    are each independently of one another C   1   -C   12   alkyl or phenyl, R   7    and R   8    are H, C   1   -C   12   alkyl, phenyl, or R   7    and R   8   , taken together, are tetramethylene, pentamethylene or  3   - oxa -   1 , 5   - pentylene, R   9    is H or C   1   -C   4   alkyl, M is H or an alkali metal, X⊖ is the anion of a monobasic acid, and * is a stereogenic carbon atom, in the form of the racemate or diastereoisomer or mixture of diastereoisomers, excluding the compound of formula I wherein R   1    is methyl and R   2    and R   3    are each cyclohexyl, and the compound of formula I wherein R   1    is methyl and the group —PR   2   R   3    is a radial of formula II.   
     
     
       17. A compound of formula I according to claim  16 , wherein R 2    and R   3    as substituted phenyl are selected from the group consisting of  2   - methylphen -   1   - yl,  3   - methylphen -   1   - yl,  4   - methylphen -   1   - yl,  2   -  or  4   - ethylphen -   1   - yl,  2   -  or  4   - isopropylphen -   1   - yl,  2   -  or  4   - tert - butylphen -   1   - yl,  2   - methoxyphen -   1   - yl,  3   - methoxyphen -   1   - yl,  4   - methoxyphen -   1   - yl,  2   -  or  4   - ethoxyphen -   1   - yl,  4   - trimethylsilyphen -   1   - yl,  2   -  or  4   - fluorophen -   1   - yl,  2 , 4   - difluorophen -   1   - yl,  2   -  or  4   - chlorophen -   1   - yl,  2 ,  4   - dichlorophen -   1   - yl,  2 , 4   - dimethylphen -   1   - yl,  3 , 5   - dimethylphen -   1   - yl,  2   - methoxy -   4   - methylphen -   1   - yl,  3 , 5   - dimethyl -   4   - methoxyphen -   1   - yl,  3 , 5   - dimethyl -   4   -( dimethylamino )- phen -   1   - yl,  2   -  or  4   - aminophen -   1   - yl,  2   -  or  4   - methylaminophen -   1   - yl,  2   -  or  4   -( dimethylamino ) phen  1   - yl,  2   -  or  4   - SO   3   H - phen -   1   - yl,  2   -  or  4   - SO   3   Na - phen -   1   - yl,  2   -  or  4   -[⊕ NH   3   Cl⊖]phen -   1   - yl,  3 , 4 , 5   - trimethylphen -   1   - yl and  2 , 4 , 6   - trimethylphen -   1   - yl.