Stereoselective Functionalization of Unsaturated Hydrocarbons

Our laboratory has developed a new approach to the stereoselective functionalization of unsaturated hydrocarbons. Traditional approaches have relied on metal-catalyzed C-H bond activation. We have devised a platform for the catalytic activation of hydrocarbons that leverages the high selectivity of pericyclic reactions. For example, we have developed a catalytic enantioselective allylic amination of unactivated alkenes via a [2,3]-rearrangement. The synthetic utility of the process is being explored by converting simple and inexpensive terminal alkenes into functional materials, such as the pharmaceutical drugs. We have also developed a copper-catalyzed enantioselective allylic alkylation of unactivated alkenes to generate alkenes with allylic stereocenters. We have discovered regioselective and diastereoselective difunctionalizatios of 1,3-dienes based on hetero-Diels-Alder reactions.  As an extension of our approach to the catalytic allylic functionalization of unactivated terminal alkenes, we recently pursued the more challenging problem of catalytic asymmetric allylic functionalization of internal alkenes. We have developed an enantioselective, regioselective, and E/Z selective allylic oxidation of unactivated internal alkenes via a catalytic asymmetric hetero-ene reaction with an imido-sulfur oxidant.