期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 55, 期 8, 页码 2764-2767出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201510540
关键词
C-C coupling; density functional calculations; oxidative coupling; reaction mechanisms; reductive elimination
资金
- ICIQ Foundation
- MINECO [CTQ2014-57661-R]
- Severo Ochoa Excellence Accreditation [SEV-2013-0319]
- ICIQ-Severo Ochoa program [SVP-2014-068662]
The reaction between benzoic acid and methylphenylacetylene to form an isocoumarin is catalyzed by Cp* Rh(OAc)(2) in the presence of Cu(OAc)(2)(H2O) as an oxidant and a leading example of oxidative-coupling reactions. Its mechanism was elucidated by DFT calculations with the B97D functional. The conventional mechanism, with separate reductive- elimination and reoxidation steps, was found to yield a naphthalene derivative as the major product by CO2 extrusion, contradicting experimental observations. The experimental result was reproduced by an alternative mechanism with a lower barrier: In this case, the copper acetate oxidant plays a key role in the reductive-elimination step, which takes place through a transition state containing both rhodium and copper centers. This cooperative reductive-elimination step would not be accessible with a generic oxidant, which, again, is in agreement with available experimental data.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据