ATROPISOMERIC ALKENYL COBALOXIMES. STEREOCHEMICAL STUDY OF THE VINYL HALIDE SUBSTITUTION BY TRANSITION-METAL COMPLEXES.

Article abstract of DOI:10.1021/ja00322a022

The first example of chiral atropisomeric cobaloximes in which the cobaloxime substituent inhibits the rotation around the naphthyl-vinyl bond is reported. These complexes were obtained by a substitution reaction of one of the enantiomers of methyl beta -chloro- beta -(2-methylnaphthyl)acrylate with cobaloxime. The reaction occurs with complete retention of the absolute configuration. A similar retention of chirality also occurs during the reaction of this beta -chloro ester with lithium dimethylcuprate. The most likely mechanism for these reactions is a direct insertion of the transition-metal atom into the carbon-halogen bond.