Catalysts based on metal complexes for the synthesis of optically active chrysanthemic acid

Abstract

Catalysts are described based on metal complexes derived from optically active s compounds, chosen from the classes consisting of bisoxazolines and salicylaldimines supported on an organic or inorganic matrix and employed in particular for the synthesis of optically active chrysanthemic acid.

1 - 42 . (canceled) 
   
   
       43 . A supported metal complex of formula (A), 
     
       
         
         
             
             
         
       
       in which Supp is polymeric type matrix, selected from polyhydrosiloxanes Met is Cu(II) or (I), L is a ligand containing at least one asymmetric carbon atom and at least one spacer chain which forms covalent bonds with said matrix, said ligand being coordinated by complexation to the aforesaid transition metal ions; said ligand L being derived from a ligand L a  chosen from the class consisting of: 
       (1) optically active bisoxazolines of the general formula (B): 
     
     
       
         
         
             
             
         
       
       and (2) optically active salicylaldimines of the general formula (C): 
     
     
       
         
         
             
             
         
       
       where: 
       *indicates a stereogenic centre, 
       R 2  and R 3 , the same or different, are chosen from: hydrogen, methyl, C 3 -C 11  alkenyl, 4-vinylbenzyl, with the proviso that at least one of the R 2  and R 3  groups has a functionality able to bind to the polymeric matrix; R 4  is H, R 5  and R 6  are the same and are selected from phenyl, naphthyl, benzyl, or R 5  and R 6  are bound together to form 1,2-indandiyl, 
       R 7  is chosen from hydrogen, methyl, tert-butyl, phenyl, vinyl phenyl, a —OR 10  group where R 10  is, C 3 -C 11  alkenyl, vinylphenyl, 4-vinylbenzyl; R 8  is chosen from methyl, benzyl; R 9  is a group of formula (D) 
     
     
       
         
         
             
             
         
       
       where R 11  is tert-butyl or tert-octyl; R 12  is n-butyl, n-octyl or C 3 -C 11  alkenyl, benzyl or 4-vinylbenzyl, with the proviso that at least one of the R 7  and R 8  groups has a functionality able to bind an already formed organic and inorganic polymer matrix. 
     
   
   
       44 . A supported metal complex of formula (A), 
     
       
         
         
             
             
         
       
       in which Supp is polymeric type matrix, selected from styrene/divinylbenzene copolymer, Met is Cu(II) or (I), L is a ligand containing at least one asymmetric carbon atom and at least one spacer chain which forms covalent bonds with said matrix, said ligand being coordinated by complexation to the aforesaid transition metal ions; said ligand L being derived from a ligand L a  chosen from the class consisting of optically active salicylaldimines of the general formula (C): 
     
     
       
         
         
             
             
         
       
       where: 
       *indicates a stereogenic centre, 
       R 7  is chosen from hydrogen, methyl, tent-butyl, phenyl, vinyl phenyl, 
       a —OR 10  group where R 10  is vinylphenyl, 4-vinylbenzyl; R 8  is chosen from methyl, benzyl; R 9  is a group of formula (D) 
     
     
       
         
         
             
             
         
       
       where R 11  is tert-butyl, or tert-octyl; R 12  is n-butyl, n-octyl, benzyl, or 4-vinylbenzyl, with the proviso that at least one of the R 7  and R 9  groups has a functionality able to bind an already formed organic and inorganic polymer matrix.