Indium-Catalysed Transfer Hydrogenation for the Reductive Cyclisation of 2-Alkynyl Enones towards Trisubstituted Furans

Abstract

Indium tribromide catalysed the transfer hydrogenation from dihydroaromatic compounds, such as the commercially available γ-terpinene, to enones, which resulted in the cyclisation to trisubstituted furan derivatives. The reaction was initiated by a Michael addition of a hydride nucleophile to the enone subunit followed by a Lewis-acid-assisted cyclisation and the formation of a furan–indium intermediate and a Wheland intermediate derived from the dihydroaromatic starting material. The product was formed by protonation from the Wheland complex and replaced the indium tribromide substituent. In addition, a site-specific deuterium labelling of the dihydroaromatic HD surrogates resulted in site specific labelling of the products and gave useful insights into the reaction mechanism by H–D scrambling.