Iridium-catalyzed Reductive Olefination of N-Methoxyamides

An iridium-catalyzed reductive olefination of N-methoxy-amides in a one-pot process is reported. The method begins with hydrosilylation of an amide carbonyl. The O-Si bond in the resulting N,Osilylacetal is then cleaved under mild conditions with TBACl to give an aldehyde, which undergoes various types of Wittig reactions in a highly stereoselective manner. The method is successfully applied to the construction of dienoates, which are widely observed in biologically active polyketides.