http://pubs.acs.org/doi/10.1021/jacs.5b09824

Complete Switch of Selectivity in the C–H Alkenylation and Hydroarylation Catalyzed by Iridium: The Role of Directing Groups

Jiyu Kim†‡, Sung-Woo Park*‡†, Mu-Hyun Baik‡†, and Sukbok Chang*‡†

† Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Korea
‡ Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 305-701, Korea

J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/jacs.5b09824
Publication Date (Web): October 8, 2015

A complete switch in the Cp*Ir(III)-catalyzed paths between C–H olefination and hydroarylation was found to be crucially dependent on the type of directing groups. This dichotomy in product distribution was correlated to the efficiency in attaining syn-coplanarity of olefin-inserted 7-membered iridacycles. Theoretical studies support our hypothesis that the degree of flexibility of this key intermediate modulates the β-H elimination, which ultimately affords the observed chemoselectivity.