Computational Exploration of Rh-III/Rh-V and Rh-III/Rh-I Catalysis in   Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides   with Alkynes

doi:10.1021/jacs.6b03424

CORC > 北京大学 > 化学与分子工程学院

	Computational Exploration of Rh-III/Rh-V and Rh-III/Rh-I Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes
	Yang, Yun-Fang ; Houk, K. N. ; Wu, Yun-Dong
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2016
关键词	CONCERTED METALATION-DEPROTONATION AB-INITIO PSEUDOPOTENTIALS MOLECULAR-ORBITAL METHODS EFFECTIVE CORE POTENTIALS INTERNAL OXIDANT BOND ACTIVATION TRANSITION-ELEMENTS POLARIZATION FUNCTIONS REDUCTIVE ELIMINATION NITROGEN-SOURCE
DOI	10.1021/jacs.6b03424
英文摘要	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 Rhy intermediate in the catalytic cycle.; National Natural Science Foundation of China [21133002, 21203004]; Shenzhen Peacock Program [KQTD201103]; National Science Foundation of the USA [CHE-1361104]; National Science Foundation under the CCI Center for Selective C-H Functionalization [CHE-1205646]; National Science Foundation [OCI-1053575]; SCI(E); EI; PubMed; ARTICLE; houk@chem.ucla.edu; wuyd@pkusz.edu.cn; 21; 6861-6868; 138
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/433746]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Yang, Yun-Fang,Houk, K. N.,Wu, Yun-Dong. Computational Exploration of Rh-III/Rh-V and Rh-III/Rh-I Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2016.
APA	Yang, Yun-Fang,Houk, K. N.,&Wu, Yun-Dong.(2016).Computational Exploration of Rh-III/Rh-V and Rh-III/Rh-I Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
MLA	Yang, Yun-Fang,et al."Computational Exploration of Rh-III/Rh-V and Rh-III/Rh-I Catalysis in Rhodium(III)-Catalyzed C-H Activation Reactions of N-Phenoxyacetamides with Alkynes".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2016).