SYNTHESIS OF AMINOPHOSPHINES CONTAINING A CHIRAL DINAPHTHOAZEPINE ENTITY AND THEIR USE IN ASYMMETRIC CATALYSIS

Three azaphospha ligands with a chiral dinaphthoazepine subunit were p repared and used in asymmetric carbon-carbon bond forming reactions. T he nickel catalyzed Grignard cross coupling reaction of 1-phenylethyl magnesium chloride and vinyl bromide afforded the product in up to 47% ee. The palladium catalyzed allylic substitution of 1,3-substituted p ropenylacetates with dimethyl malonate and the coupling of allylacetat e with methyl N-(diphenylmethylene)-glycinate resulted in asymmetric i nductions of up to 97% ee and 51% ee, respectively.