Experimental and Computational Investigations of the Reactions between α,β-Unsaturated Lactones and 1,3-Dienes by Cooperative Lewis Acid/Brønsted Acid Catalysis

Abstract

The reactions of α,β-unsaturated δ-lactones with activated dienes such as 1,3-dimethoxy-1-[(trimethylsilyl)oxy]-1,3-butadiene (Brassard's diene) are barely known in literature and show high potential for the synthesis of isocoumarin moieties. An in-depth investigation of this reaction proved a stepwise mechanism via the vinylogous Michael-products. Subsequent cyclisation and oxidation by LHMDS and DDQ, respectively, provided six mellein derivatives (30-84 %) and four angelicoin derivatives (40-78 %) over three steps. DFT-calculations provide insights into the reaction mechanism and support the theory of a stepwise reaction.

Keywords: Michael additions; catalysis; computational chemistry; density functional calculations; natural products.