Iridium-Catalyzed Aerobic α,β-Dehydrogenation of γ,δ-Unsaturated Amides and Acids: Activation of Both a- and β-C-H bonds through an Allyl-Iridium Intermediate

摘要

Direct aerobic α,β-dehydrogenation of γ,δ-unsaturated amides and acids using a simple iridium/copper relay catalysis system is described. We developed a new strategy that overcomes the challenging issue associated with the low α-acidity of amides and acids. Instead of α-C–H metalation, this reaction proceeds by β-C–H activation, which results in enhanced α-acidity. Conjugated dienamides and dienoic acids were synthesized in excellent yield with this reaction, which uses a simple reaction protocol. Mechanistic experiments suggest a catalyst resting state mechanism in which both α-C–H and β-C–H cleavage is accelerated.