Enantioselective hydrogenation of 4-substituted 1,2-dihydroquinolines in presence of a chiral iridium catalyst

Abstract

The invention relates to a process for preparing optically active 4-substituted 1,2,3,4-tetrahydroquinolines comprising enantioselective hydrogenation of the corresponding 4-substituted 1,2-dihydroquinolines in presence of a chiral iridium (P,N)-ligand catalyst.

1 : A process for preparing a compound of the formula (Ia) or (b), 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 6 -C 14 -aryl, or C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl and the C 1 -C 6 -alkoxy in the C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl moiety, are optionally substituted by 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl may be substituted by one to five substituents selected independently from each other from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy, and 
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, 
 
         R 2  and R 3  are the same and are selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl and C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, or 
         R 2  and R 3  together with the carbon to which they are bonded, form a C 3 -C 6 -cycloalkyl ring, 
         R 4  is hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylamino, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl, C 2 -C 6 -alkenyloxy, 9-flurorenylmethyleneoxy, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy, C 6 -C 14 -aryl-C 1 -C 4 -alkyloxy or C 6 -C 4 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl as such or as part of a composite substituent is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, 
 
         n is 0, 1, 2, 3 or 4, 
         each substituent R 5 , if present, is independently selected from the group consisting of halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, hydroxyl, amino and —C(═O)—C 1 -C 6 -alkyl, 
         comprising enantioselective hydrogenation of a compound of the formula (II) 
       
       
         
           
           
               
               
           
         
         wherein the substituents R 1 , R 2 , R 3 , R 4 , R 5  and the integer n are each as defined for the compound of the formula (a) or (b), 
         in presence of a chiral iridium catalyst, 
         characterized in that the chiral iridium catalyst comprises a chiral ligand of the formula (IIIa), (IIIb), (IVa) or (IVb), 
       
       
         
           
           
               
               
           
         
         wherein 
         R 6 , R 7  and R 8  are independently from one another selected from hydrogen, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 7 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, C 6 -C 14 -aryl and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 7 -cycloalkyl and the C 3 -C 7 -cycloalkyl in the C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl moiety are optionally substituted by 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkyl and C 1 -C 4 -haloalkoxy, and 
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety are optionally substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl again is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents, 
 
         R 9  and R 10  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkoxy, di(C 1 -C 6 -alkyl)amino, C 3 -C 12 -cycloalkyl, C 3 -C 12 -cycloalkyl-C 1 -C 4 -alkyl, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkoxy and di(C 1 -C 6 -alkyl)amino are optionally substituted by 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl may be substituted by one to five substituents selected independently from each other from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy, and 
 wherein the C 6 -C 14 -aryl, C 6 -C 14 -aryloxy and C 3 -C 12 -cycloalkyl, in each case as such or as part of a composite substituent, are optionally substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents or 
 
         R 9  and R 10  together with the phosphorus atom to which they are bonded, form a phospholane ring, which may be substituted with one or two C 1 -C 6 -alkyl groups, or 
         R 9  and R 10  together form 
       
       
         
           
           
               
               
           
         
         
           where the bonds identified by “x” and “y” are both bonded directly to the phosphorus atom, 
         
         p and q are independently from one another selected from 0, 1 and 2, 
         R 11  and R 12  are independently selected from C 1 -C 6 -alkyl and phenyl, which may be substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy and phenyl, which may be substituted by one or two C 1 -C 4 -alkyl substituents, 
         m is 1 or 2, 
         A is 
       
       
         
           
           
               
               
           
         
         
           where the bond identified by “*” is bonded directly to the phosphorus atom and where the bond identified by “#” is bonded directly to the oxazoline moiety, 
         
         R 13  is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 2 -cycloalkyl, C 3 -C 2 -cycloalkyl-C 1 -C 4 -alkyl, C 1 -C 4 -alkyl-C 3 -C 7 -cycloalkyl, C 6 -C 14 -aryl or C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, 
 
         R 14  and R 15  are independently from one another selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 12 -cycloalkyl, C 3 -C 7 -cycloalkyl-C 1 -C 4 -alkyl, C 1 -C 4 -alkyl-C 3 -C 7 -cycloalkyl, C 6 -C 14 -aryl and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or 
 
         R 14  and R 15  together with the carbon to which they are bonded, form a C 5 -C 6 -cycloalkyl ring, 
         R 16  and R 17  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkoxy, di(C 1 -C 6 -alkyl)amino, C 3 -C 12 -cycloalkyl, C 3 -C 12 -cycloalkyl-C 1 -C 4 -alkyl, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkoxy, C 1 -C 6 -cycloalkyl and di(C 1 -C 6 -alkyl)amino are optionally substituted by 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl may be substituted by one to five substituents selected independently from each other from halogen, C 1 -C 4 -alkyl, phenyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy, and 
 wherein the C 6 -C 14 -aryl, the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl, the C 6 -C 14 -aryloxy and C 3 -C 12 -cycloalkyl, in each case as such or as part of a composite substituent, are optionally substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, phenyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or 
 
         R 16  and R 17  together with the phosphorus atom to which they are bonded, form a phospholane ring, which may be substituted with one or two C 1 -C 6 -alkyl groups or 
         R 16  and R 17  together form G 1  or G 2 , wherein G 1  and G 2  are as defined for the substituents R 9  and R 10  of the ligands of the formulae (IIIa) and (IIIb). 
       
     
     
         2 : The process according to  claim 1 , wherein
 R 1  is C 1 -C 6 -alkyl or C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy 
   R 2  and R 3  are the same and are selected from C 1 -C 4 -alkyl,   R 4  is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, phenyl or benzyl,   n is 0, 1 or 2, and   each substituent R 5 , if present, is independently selected from the group consisting of halogen, C 1 -C 6 -alkyl and C 1 -C 6 -haloalkyl.   
     
     
         3 : The process according to  claim 1 , wherein
 R 1  is methyl, ethyl or n-propyl,   R 2  and R 3  are methyl,   R 4  is C 1 -C 4 -alkyl,   n is 0, 1 or 2, and   each substituent R 5 , if present, is independently selected from the group consisting of halogen and C 1 -C 6 -alkyl.   
     
     
         4 : The process according to  claim 1 , wherein the chiral iridium catalyst comprises a chiral ligand of the formula (IIa) or (IIIb), wherein
 R 6  is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 7 -cycloalkyl or C 6 -C 14 -aryl,
 wherein the C 6 -C 14 -aryl is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl again is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents, 
   R 7  and R 8  are independently from one another selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 6 -C 14 -aryl or C 1 -C 6 -haloalkyl,
 wherein the C 6 -C 14 -aryl is unsubstituted or substituted by one to five C 1 -C 4 -alkyl substituents, 
   R 9  and R 10  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, di(C 1 -C 6 -alkyl)amino, C 3 -C 12 -cycloalkyl, C 6 -C 14 -aryl, C 6 -C 14 -aryloxy and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy and di(C 1 -C 6 -alkyl)amino moieties are optionally substituted by 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl may be substituted by one to five substituents selected independently from each other from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy, and 
 wherein the C 6 -C 14 -aryloxy, C 3 -C 12 -cycloalkyl and C 6 -C 14 -aryl, as such or as part of a composite substituent, in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents, or 
   R 9  and R 10  together with the phosphorus atom to which they are bonded, form a phospholane ring, which may be substituted with one or two C 1 -C 6 -alkyl groups,   m is 1 or 2,   or the chiral iridium catalyst comprises a chiral ligand of the formula (IVa) or (IVb), wherein   A is   
       
         
           
           
               
               
           
         
         
           where the bond identified by “*” is bonded directly to the phosphorus atom and where the bond identified by “#” is bonded directly to the oxazoline moiety, 
         
         R 13  is C 3 -C 6 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 14 -aryl or C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, 
 
         R 14  and R 15  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, C 6 -C 14 -aryl, C 3 -C 12 -cycloalkyl, and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or 
 
         R 14  and R 15  together with the carbon to which they are bonded, form a C 5 -C 6 -cycloalkyl ring, and 
         R 16  and R 17  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 14 -aryl and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 1 -C 6 -alkyl is optionally substituted by 1 to 3 substituents independently selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 -haloalkoxy and phenyl, wherein the phenyl may be substituted by one to five substituents selected independently from each other from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, and C 1 -C 4 -haloalkoxy, and 
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, phenyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or 
 
         R 16  and R 17  together with the phosphorus atom to which they are bonded, form a phospholane ring, which may be substituted with one or two C 1 -C 6 -alkyl groups. 
       
     
     
         5 : The process according to  claim 1 , wherein the chiral iridium catalyst comprises a chiral ligand of the formula (IIa) or (IIIb), wherein
 R 6  is selected from the group consisting of 1-naphtyl, 2-naphtyl, 9-antracenyl, 9-phenantryl or phenyl, which is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and phenyl, wherein the phenyl again is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents,   R 7  and R 8  are independently from one another hydrogen or C 1 -C 6 -alkyl,   R 9  and R 10  are independently from one another selected from the group consisting of ethyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl and benzyl, and   m is 1 or 2,   or the chiral iridium catalyst comprises a chiral ligand of the formula (IVa) or (IVb), wherein   A is   
       
         
           
           
               
               
           
         
         
           where the bond identified by “*” is bonded directly to the phosphorus atom and where the bond identified by “#” is bonded directly to the oxazoline moiety, 
         
         R 13  is selected from the group consisting of C 3 -C 6 -alkyl, C 3 -C 2 -cycloalkyl, C 6 -C 14 -aryl or C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen or C 1 -C 4 -alkyl, 
 
         R 14  and R 15  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen and C 1 -C 4 -alkyl, and 
 
         R 16  and R 17  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, C 3 -C 12 -cycloalkyl, C 6 -C 14 -aryl and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl and the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl, phenyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, or 
 
         R 16  and R 17  together with the phosphorus atom to which they are bonded, form a phospholane ring, which may be substituted with one or two C 1 -C 6 -alkyl groups. 
       
     
     
         6 : The process according to  claim 1 , wherein the hydrogenation is conducted using hydrogen gas at a pressure of from 1 to 300 bar. 
     
     
         7 : The process according to  claim 1 , wherein the amount of iridium catalyst used is within the range of from 0.001 mol % to 5 mol %, based on the amount of the compound of the formula (II). 
     
     
         8 : The process according to  claim 1 , wherein the hydrogenation is conducted at a temperature within the range of from 20° C. to 130° C. 
     
     
         9 : The process according to  claim 1 , wherein the hydrogenation is conducted in presence of a solvent selected from the group consisting of 2,2,2,-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 1,2-dichloroethane, tetrafluoropropanol, and mixtures thereof. 
     
     
         10 : The process according to  claim 1 , wherein the chiral iridium catalyst has the general formula (Va), (Vb), (VIa) or (VIb): 
       
         
           
           
               
               
           
         
         wherein 
         R 6  is selected from the group consisting of 1-naphtyl, 2-naphtyl, 9-antracenyl, 9-phenantryl or phenyl,
 wherein 1-naphtyl, 2-naphtyl, 9-antracenyl, 9-phenantryl and phenyl are unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and phenyl, wherein the phenyl again is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents, 
 
         R 7  and R 8  are independently from one another hydrogen or C 1 -C 6 -alkyl, 
         R 9  and R 10  are independently from one another selected from the group consisting of ethyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl and benzyl, 
         m is 1 or 2, 
         R 13  is iso-propyl, sec-butyl, iso-butyl, tert-butyl, phenyl or benzyl, 
         R 14  and R 15  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen and C 1 -C 4 -alkyl, 
 
         R 16  and R 17  are independently from one another phenyl, 1-naphthyl or 2-naphthyl, which in each case is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkyl and C 1 -C 4 -haloalkyl, and 
         R 18  is phenyl, which is unsubstituted or substituted with one to five substituents selected from fluorine and C 1 -C 4 -haloalkyl. 
       
     
     
         11 : The process according to  claim 10 , wherein
 R 6  is selected from the group consisting of phenyl, 2,6- or 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 3,5-bis-tert-butyl-4-methoxyphenyl, 4-tert-butyl-2,6-dimethylphenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 1-naphtyl, 9-antracenyl 2,4,6-triisopropylphenyl, 9-phenantryl or 2,6-diethyl-4-methylphenyl,   R 7  is hydrogen,   R 8  is hydrogen or methyl,   R 9  and R 10  are each the same and tert-butyl, adamantly, cyclopentyl or cyclohexyl,   m is 1 or 2,   R 13  is tert-butyl,   R 14  and R 15  are methyl,   R 16  and R 17  are independently from one another phenyl, which is substituted by one or two methyl, in particular R 16  and R 17  are each the same and 2-methylphenyl or
 3,5-dimethylphenyl, and 
   R 18  is 3,5-bis(trifluoromethyl)phenyl.   
     
     
         12 : The process according to  claim 1 , wherein the chiral iridium catalyst comprises a chiral ligand of the formula (IIIa) or (IIIb), wherein
 R 6  is selected from the group consisting of 1-naphtyl, 2-naphtyl, 9-antracenyl, 9-phenantryl or phenyl, which is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and phenyl, wherein the phenyl again is unsubstituted or substituted by one to five C 1 -C 6 -alkyl substituents,   R 7  and R 8  are independently from one another hydrogen or C 1 -C 6 -alkyl,   R 9  and R 10  are independently from one another selected from the group consisting of ethyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl and benzyl, and   m is 1 or 2.   
     
     
         13 : The process according to  claim 12 , wherein
 R 6  is selected from the group consisting of phenyl, 2,6- or 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 3,5-bis-tert-butyl-4-methoxyphenyl, 4-tert-butyl-2,6-dimethylphenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 1-naphtyl, 9-antracenyl 2,4,6-triisopropylphenyl, 9-phenantryl or 2,6-diethyl-4-methylphenyl,   R 7  is hydrogen   R 8  is hydrogen or methyl,   R 9  and R 10  are each the same and tert-butyl, cyclopentyl or cyclohexyl, and   m is 1.   
     
     
         14 : The process according to  claim 1 , wherein the chiral iridium catalyst comprises a chiral ligand of the formula (IVa) or (IVb), wherein
 A is   
       
         
           
           
               
               
           
         
         
           where the bond identified by “*” is bonded directly to the phosphorus atom and where the bond identified by “#” is bonded directly to the oxazoline moiety, 
         
         R 13  is iso-propyl, sec-butyl, iso-butyl, tert-butyl, phenyl or benzyl, 
         R 14  and R 15  are independently from one another selected from the group consisting of C 1 -C 6 -alkyl, and C 6 -C 14 -aryl-C 1 -C 4 -alkyl,
 wherein the C 6 -C 14 -aryl in the C 6 -C 14 -aryl-C 1 -C 4 -alkyl moiety is unsubstituted or substituted by one to five substituents selected from the group consisting of halogen and C 1 -C 4 -alkyl, 
 
         R 16  and R 17  are independently from one another phenyl, 1-naphthyl or 2-naphthyl, which in each case is unsubstituted or substituted by one to five C 1 -C 4 -alkyl substituents. 
       
     
     
         15 : The process according to  claim 14 , wherein
 R 13  is tert-butyl,   R 14  and R 15  are methyl, and   R 16  and R 17  are independently from one another phenyl, which is substituted by one or two methyl groups.   
     
     
         16 : The process according to  claim 1 , wherein the chiral iridium catalyst comprises a chiral ligand of the formula (IIIa) or (IIIb), wherein
 R 6  is selected from the group consisting of phenyl, 2,6- or 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 4-tert-butylphenyl, 4-methoxyphenyl, 3,5-bis-tert-butyl-4-methoxyphenyl, 4-tert-butyl-2,6-dimethylphenyl, 4-fluorophenyl, 4-trifluoromethylphenyl, 1-naphtyl, 9-antracenyl, 2,4,6-triisopropylphenyl, 9-phenantryl and 2,6-diethyl-4-methylphenyl,   R 7  is hydrogen,   R 8  is C 1 -C 6 -alkoxy,   R 9  and R 10  are independently from one another selected from the group consisting of ethyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, cyclohexyl, cyclopentyl, adamantyl and benzyl, and   m is 1.