α,β-Unsaturated acyl cyanide synthesis via triethylamine catalyzed redox cyanation

Stereoselective redox cyanation of alkynyl aldehydes was explored, furnishing (E)-alpha,beta-unsaturated acyl cyanides. This reaction was catalyzed by mild TEA base, as a dual role of Lewis base and Bronsted base. TMSCN treated with TEA was an effective reagent for generating umpolung intermediates from alkynyl aldehydes, and this nucleophilic intermediate can be protonated by equimolar amount of EtOH, promoting the efficient conversion into alpha,beta-unsaturated acyl cyanides. The synthesized acyl cyanides were successfully applied as the synthetic precursors in the iron-catalyzed arylation reactions. (C) 2011 Elsevier Ltd. All rights reserved.