New Methods for the Synthesis of Vinyl Azides

Abstract

Abstract A critical survey of synthetic approaches to vinyl azides is presented, focusing especially on stereo‐ and regiochemical problems. The com bined procedure of azidohalogenation of olefins followed by dehydrohalogenation, leads to regiospecific and, in the case of ionic additions, also to stereospecific formation of vinyl azides. Nucleophilic substitutions by azide ions on activated olefinic halides result in β‐azidovinyl ketones, esters, nitriles, etc., and proceed predominantly with retention of configuration about the CC bond. The known synthetic methods leading to α‐azidovinyl ketones and esters give rise to the thermodynamically more stable trans‐vinyl azides.