Regioselective Cobalt-Catalyzed Diels-Alder Reaction towards 1,3-Disubstituted and 1,2,3-Trisubstituted Benzene Derivatives

Abstract

A straightforward reaction sequence consisting of the Wittig olefination of aldehydes utilizing allyltriphenylphosphonium bromide for the generation of 1-substituted 1,3-dienes, cobalt-catalyzed neutral Diels-Alder reaction with terminal and internal alkynes, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of the dihydroaromatic intermediates leads to regiochemically enriched biphenyl, terphenyl, and silyl-functionalized benzene derivatives in good to excellent yields. Starting from a 1,3-diyne and a 1,3-diene, the reaction sequence consisting of cobalt-catalyzed Diels-Alder reaction, DDQ oxidation, and cobalt-catalyzed cyclotrimerization with acetylene gave an axially chiral biphenyl-terphenyl product.

Key words

alkyne - cobalt - Diels-Alder - diene - Wittig olefination

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