The Bruylants and related reactions.

This review focuses on the Bruylants reaction, namely the substitution with Grignard reagents of the cyano group in α-aminonitriles. This reaction goes through an iminium ion intermediate and proceeds with excellent stereoselectivities. The extension to organozinc reagents has been successfully applied. Triazoles such as benzotriazole and especially 1,2,3-triazole appear as relevant substitutes for the cyano leaving group. An alternative pathway for substitution of the cyano group involves an α-alkylation-decyanation sequence. Selected applications in organic synthesis are proposed. [ABSTRACT FROM AUTHOR]