Catalytic generation of activated carboxylates from enals: a product-determining role for the base

Abstract

N-Heterocycle carbenes generated in situ from imidazolium or triazolium salts and bases react with enals, leading to the catalytic generation of homoenolates. The fate of these intermediates is determined by the catalytic base: strong bases such as (t)BuOK lead to carbon-carbon bond formation, while weaker bases allow protonation of the homoenolate and subsequent generation of activated carboxylates. This discovery, along with the design of a new triazolium precatalyst, enables the catalytic, atom-economical redox esterification of enals. [reaction: see text]