Lab of Computational Chemistry and Drug Design, Laboratory of Chemical Genomics, Peking University Shenzhen Graduate School , Shenzhen 518055, China.
Department of Chemistry and Biochemistry, University of California , Los Angeles, California 90095, United States.
J Am Chem Soc. 2016 Jun 1;138(21):6861-8. doi: 10.1021/jacs.6b03424. Epub 2016 May 23.
The selective rhodium-catalyzed functionalization of arenes is greatly facilitated by oxidizing directing groups that act both as directing groups and internal oxidants. We report density functional theory (B3LYP and M06) investigations on the mechanism of rhodium(III)-catalyzed redox coupling reaction of N-phenoxyacetamides with alkynes. The results elucidated the role of the internal oxidizing directing group, and the role of Rh(III)/Rh(I) and Rh(III)/Rh(V) catalysis of C-H functionalizations. A novel Rh(III)-Rh(V)-Rh(III) cycle successfully rationalizes recent experimental observations by Liu and Lu et al. ( Liu , G. Angew. Chem. Int. Ed. 2013 , 52 , 6033 ) on the reactions of N-phenoxyacetamides with alkynes in different solvents. Natural Bond Orbital (NBO) analysis confirms the identity of Rh(V) intermediate in the catalytic cycle.
芳基的选择性铑催化功能化反应可以通过氧化导向基团得到极大促进，这些氧化导向基团既可以作为导向基团，也可以作为内部氧化剂。我们报告了密度泛函理论（B3LYP 和 M06）对 N-苯氧乙酰酰胺与炔烃的铑（III）催化氧化偶联反应机理的研究。结果阐明了内部氧化导向基团的作用，以及 Rh(III)/Rh(I)和 Rh(III)/Rh(V)催化 C-H 官能化的作用。一个新的 Rh(III)-Rh(V)-Rh(III)循环成功地解释了 Liu 和 Lu 等人（Liu，G. Angew. Chem. Int. Ed. 2013, 52, 6033）最近关于 N-苯氧乙酰酰胺与炔烃在不同溶剂中反应的实验观察结果。自然键轨道（NBO）分析证实了催化循环中 Rh(V)中间体的身份。
