The Bruylants and related reactions

Abstract

This review focuses on the Bruylants reaction, namely the substitution with Grignard reagents of the cyano group in -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 -alkylation-decyanation sequence. Selected applications in organic synthesis are proposed.

Primary α-Phosphino- and α-Arseno-Nitriles, Analogues of α-Aminonitriles

“…α-Aminonitriles have been synthesized in the mid-19th century by Adolph Strecker using a multicomponent reaction . Primary α-aminonitriles are well-known and well-studied compounds involved in numerous reactions, and precursors of various species such as amino acids by acid hydrolysis, amines via a Bruylants reaction or imines by basic dehydrocyanation. − They probably played a key role on the Primitive Earth − and the simplest derivative, aminoacetonitrile, has been detected in the interstellar medium . To our knowledge, the corresponding phosphorus and arsenic derivatives have not yet been synthesized, whereas numerous functionalized phosphines and arsines were synthesized shortly after the nitrogen derivatives, such as vinylamine, , vinylphosphine and vinylarsine .…”