Transition metal catalyzed regioselective carbon-carbon bond formation mediated by transfer hydrogenation

One of the more formidable challenges in the synthesis of complex organic molecules remains the efficient formation of carbon-carbon bonds. The development of a broad class of reactions to achieve this goal involves the addition of carbon based nucleophiles to carbonyl and imine compounds. Until recently, classical approaches to carbon-carbon bond formation generally required the use of stoichiometric pre-formed organometallic reagents to serve as nucleophiles, which translate into stoichiometric organometallic byproducts. In an effort to minimize nucleophile pre-activation and byproduct formation, our lab has developed efficient methods for carbonyl and imine additions via in situ formation of alkyl metal nucleophiles from π-unsaturates. The research reported herein describes our advances in an assortment of transition metal-catalyzed carbon-carbon bond forming reactions mediated by transfer hydrogenation, including regioselective hydrohydroxymethylation, hydrohydroxyfluoroalkylation, and hydroaminomethylation. Additionally, the investigation of regioselective carbonyl vinylation is reported.