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Cover image for Vol. 80 Issue 7

Editor: Marisa Spiniello

Impact Factor: 3.026

ISI Journal Citation Reports © Ranking: 2014: 43/157 (Chemistry Multidisciplinary)

Online ISSN: 2192-6506

Associated Title(s): Angewandte Chemie International Edition, Chemistry - A European Journal

Full Paper: Computational Studies on the Mechanism of the Copper-Catalyzed sp3-C-H Cross-Dehydrogenative Coupling Reaction

Gui-Juan Cheng, Li-Juan Song, Yun-Fang Yang, Xinhao Zhang, Olaf Wiest, Yun-Dong Wu

09_300117/2013Issue 09/2013, pp. 943-951

A detailed computational study of a copper-catalyzed aerobic cross-dehydrogenative coupling reaction has been conducted. To select a reliable method to describe the thermochemistry of a single electron transfer (SET) process, benchmark calculations have been performed. M06/6-311+g(d,p) is appropriate to evaluate the thermochemistry of the SET process for the system involving iminium species. The computational results support an SET mechanism, but also uncover an alternative mechanism in which O2 is directly involved in a hydrogen-abstracting step. A comparative study with tert-butylhydroperoxide (TBHP) as the oxidant has also been performed. The computations reveal several competitive pathways, including a radical pathway, a CuIII pathway, and an SET mechanism for the Cu/TBHP system.

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