We have been exploring the selective functionalization of unactivated olefins. As a first step towards this goal, we have developed a catalytic enantioselective allylic amination of unactivated olefins via a [2,3]-rearrangement. In this method, a diimido-sulfur reagent serves as the source of nitrogen, and it reacts selectively with terminal olefins through a hetero-ene reaction. The resulting zwitterionic ene adduct undergoes a Pd-catalyzed enantioselective [2,3]-rearrangement to generate chiral amines in high enantiomeric excess. Our approach is conceptually distinct from other enantioselective allylic amination strategies. Based on this chemistry, we have also developed a copper-catalyzed allylic alkylation of unactivated olefins and dienes. This represents a general method for functionalizing unactivated olefins with aromatic, aliphatic, and vinyl Grignard reagents. Our recent discoveries represent a conceptual framework for the generalized functionalization of unactivated olefins. References 1. Hongli Bao, Xiangbing Qi, and Uttam K. Tambar. J. Am. Chem. Soc. 2011 , 133, 1206-1208.2. Hongli Bao, Xiangbing Qi, and Uttam K. Tambar. Synlett 2011 , 1789-1792.3. Hongli Bao and Uttam K. Tambar. J. Am. Chem. Soc. 2012 , 134, 18495-18498.

Allylic functionalization of unactivated olefins

247th National Meeting (2014)

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