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The 20th ESICB Colloquium
(Elements Strategy Initiative for Catalysts and Batteries)
Speaker: Dr. Xiaoguang Bao
(College of Chemistry, Chemical Engineering and Materials Science, Soochow University, 199 Ren-Ai Road, Suzhou Industrial Park, Suzhou, Jiangsu 215123, China)
Title: “Mechanistic Insights on the Transition-Metal-
Catalyzed C-H Amination Reactions Based on DFT Studies”
Date and Time: February 26 (Mon), 2018; 15:00 to 16:00 Place: Seminar Room, Innovation Plaza 1F, Katsura Campus,
Kyoto University (京大桂キャンパス イノベーションプラザ１Ｆセミナー室)
本件連絡先：触媒・電池元素戦略ユニット事務室 ([email protected])
Abstract: Direct construction of C-N bond via C-H activation using insertion of nitrene group has fascinated significant interest because catalytic C-N bond formation is crucially important in organic synthesis. In comparison with substrates containing reactive allylic and benzylic C-H bonds, it is more challenging to insert a nitrene group into unactivated aromatic C-H bond. In this talk, I would like to present our recent work on the density functional theory (DFT) studies of the mechanistic difference between the aromatic sp2 C-H bond amination and alkyl sp3 C-H bond amination. Also, I wish to show computational studies shed light on mechanistic insights for the origin of the chemoselective C-H bond amination using the Cu and Au catalysts. In addition, computational studies were carried out to explore the mechanism of Pd-catalyzed intermolecular C–H amination with O-benzoyl hydroxylamines, in which both Pd(0) and Pd(II) catalysts are effective. For the Pd(0)-catalyzed reaction, the generally assumed Pd(0)/Pd(II) catalytic cycle might not be feasible. Instead, the Pd(0), being essentially a catalyst precursor, could be oxidized to Pd(II) and the C–H amination proceeds through the Pd(II)/Pd(IV) catalytic cycle.
