title: Cp*Ir(III)-Catalyzed Mild and Broad C-H Arylation of Arenes and Alkenes with Aryldiazonium Salts Leading to the External Oxidant-Free Approach.
abstract: Reported herein is the development of Cp*Ir(III)-catalyzed direct C-H arylation of arenes and alkenes using aryldiazonium tetrafluoroborates, the use of which as an aryl precursor and also as an oxidant via C-N2 bond cleavage was a key to success in achieving a mild and external oxidant-free procedure. Mechanistic experiments and DFT calculations revealed the turnover-limiting step to be closely related to the formation of an Ir(V)-aryl intermediate rather than the presupposed C-H cleavage. Under the developed mild arylation conditions, a wide range of benzamides were smoothly arylated. In addition, synthetic utility of the current C-H arylation procedure was also demonstrated successfully for the (Z)-selective arylation of enamides and C8-selective reaction of quinoline N-oxides.
authors.affiliation: †Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea.|‡Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon 305-701, Republic of Korea.
authors.forename: Kwangmin
authors.initials: K
authors.lastname: Shin
authors.affiliation: †Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701, Republic of Korea.|‡Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon 305-701, Republic of 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, Republic of Korea.|‡Center for Catalytic Hydrocarbon Functionalization, Institute for Basic Science (IBS), Daejeon 305-701, Republic of Korea.
authors.forename: Sukbok
authors.initials: S
authors.lastname: Chang