A silicon‐assisted synthesis of (E)‐β‐haloenamides from N‐vinylamides

(E)-β-Iodoenamides and (E)-β-iodoenimides can be easily obtained from N-vinyl derivatives (N-vinylamides and N-vinylimides) by stereoselective ruthenium-catalysed silylative coupling with vinyltrimethylsilane (Marciniec coupling) and subsequent stereospecific silicon–iodine exchange. Bromodesilylation of (E)-β-silylenimides affords (E)-β-bromoenimides, while the analogous reactions involving (E)-β-silylenamides lead to decomposition of substrates. N-Halosuccinimides have been found as the most effective halogenating agents in the desilylation step under mild conditions. The ruthenium-catalysed silylation/halodesilylation sequence can be performed in a one-pot procedure. Copyright © 2015 John Wiley & Sons, Ltd.