Nickel catalyzed cross-coupling reactions between organomagnesium compounds and anisole derivatives

Abstract

The present invention provides nickel catalysts and solvents which are useful in a cross-coupling reaction between an organomagnesium compound and an aromatic ether compound, such as an anisole derivative.

1 . A catalyst composition comprising one equivalent of a nickel catalyst of the formula:  
     
       
         
         
             
             
         
       
     
     and at least two equivalents of a phosphine compound of the formula:  
       PR 3 R 4 R 5 , (R 4a )(R 5a )P—R 3a —P(R 4b )(R 5b ) or a mixture thereof, 
     wherein 
 each of a and b is independently an integer from 0 to 2;  
 c is an integer from 0 to 4;  
 provided that the sum of a+b+c is such that the total nickel metal coordination number is 2 or 4;  
 each X 2  is independently a co-ligand;  
 R 3a  is alkylene;  
 each of R 3 , R 4 , R 4a  and R 4b  is independently a saturated hydrocarbon moiety having from one to about twelve carbon atoms; and  
 each of R 5 , R 5a  and R 5b  is selected from a saturated hydrocarbon moiety having from one to about twelve carbon atoms and an aryl moiety having from six to fourteen carbon ring atoms.  
 
   
   
       2 . The catalyst composition of  claim 1 , wherein the nickel catalyst is of the formula:  
       (X 2 ) 2 Ni(PR 6 R 7 R 8 ) 2   
     wherein 
 each X 2  is independently a co-ligand;  
 R 6  is cycloalkyl; and  
 each of R 7  and R 8  is independently selected from the group consisting of a saturated hydrocarbon moiety having from one to about twelve carbon atoms and an aryl moiety having from six to fourteen carbon atoms.  
 
   
   
       3 . The catalyst composition of  claim 2 , wherein the phosphine compound is of the formula:  
       PR 6 R 7 R 8   
     wherein 
 R 6  is cycloalkyl; and  
 each of R 7  and R 8  is independently selected from the group consisting of a saturated hydrocarbon moiety having from one to about twelve carbon atoms and an aryl moiety having from six to fourteen carbon atoms.  
 
   
   
       4 . The catalyst composition of  claim 3 , wherein each of R 7  and R 8  is independently a saturated hydrocarbon moiety having from one to about twelve carbon atoms.  
   
   
       5 . The catalyst composition of  claim 4 , wherein each saturated hydrocarbon is independently selected from the group consisting of C 1 -C 12  alkyl and C 3 -C 10  cycloalkyl.  
   
   
       6 . The catalyst composition of  claim 5 , wherein each of R 7  and R 8  is independently C 3 -C 10  cycloalkyl.  
   
   
       7 . The catalyst composition of  claim 6 , wherein each of the co-ligand is independently selected from the group consisting of halide, carboxylate, sulfonate, and 1,3-diketone.  
   
   
       8 . The catalyst composition of  claim 7 , wherein each of the co-ligand is independently halide.  
   
   
       9 . The catalyst composition of  claim 8 , wherein R 6 , R 7  and R 8  are cyclohexyl and X 2  is chloride.