title: Complete Switch of Selectivity in the C-H Alkenylation and Hydroarylation Catalyzed by Iridium: The Role of Directing Groups.
abstract: 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.
authors.affiliation: 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.
authors.forename: Jiyu
authors.initials: J
authors.lastname: Kim
authors.affiliation: 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.
authors.forename: Sung-Woo
authors.initials: SW
authors.lastname: Park
authors.affiliation: 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.
authors.forename: Mu-Hyun
authors.initials: MH
authors.lastname: Baik
authors.affiliation: 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.
authors.forename: Sukbok
authors.initials: S
authors.lastname: Chang