Diverted Telomerization Reaction with Aryl Boronic Derivatives: Expeditious Synthesis of Aryl-Substituted 1,6-and 1,7-dienes

Abstract

[EN] The telomerization reaction is a fundamental transformation in industry for the synthesis of highly substituted medium linear carbon chain products (8-12 carbon atoms) with heteroatoms (typically oxygen and nitrogen atoms). Here we show that this multibond forming reaction can be interrupted by adding an aryl boronic derivative in the reaction mixture, which diverts the reaction pathway from the final heteroatom toward the aryl coupling to give aryl-substituted 1,6- and 1,7-dienes in a very simple manner. Carbon chains between 14 and 30 carbon atoms can be prepared. Experimental and computational studies support a reaction mechanism that combines the classical telomerization reaction during the first steps and the Tsuji-Trost reaction for the last steps. These results open the way to designing different telomerization reactions where the final coupled fragment is not a canonical nucleophile.