LAUSR

A single and accessible cationic iridium III metallacycle catalyzes effectively the one-pot sequential double hydrosilylation of challenging -unsaturated secondary and tertiary amides to afford in a controlled and straightforward way the corresponding reduced products, that is to say the related secondary and tertiary amides and amines. The catalytic hydrosilylations of the conjugated amides described herein proceeded in good yields and high chemoselectivities. The critical silyl enolate, in other words silyl ketene aminal intermediate, has been observed and characterized by using control experiments, mass spectrometry and state of the art Nuclear Magnetic Resonance analyses. The present achievements indicate a promising potential of catalysts based on metallacycles for future significant developments in one-pot multicatalytic synthesis and therefore the production of highly functionalized and complex organic molecules.