Bifunctional Ligand-Assisted Catalytic Ketone alpha-Alkenylation with   Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies

doi:10.1021/jacs.5b10466

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	Bifunctional Ligand-Assisted Catalytic Ketone alpha-Alkenylation with Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies
	Mo, Fanyang ; Lim, Hee Nam ; Dong, Guangbin
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2015
关键词	C-H BOND CONIA-ENE REACTION 2-ALKYNIC 1,3-DICARBONYL COMPOUNDS ACTIVE METHYLENE-COMPOUNDS BETA-KETOESTERS COOPERATIVE CATALYSIS UNSATURATED-KETONES CARBONYL-COMPOUNDS TERMINAL ACETYLENES SIMPLE OLEFINS
DOI	10.1021/jacs.5b10466
英文摘要	Here, we describe a detailed study of the rhodium(I)-catalyzed, bifunctional ligand-assisted ketone alpha-C-H alkenylation using internal alkynes. Through controlling the reaction conditions, conjugated enamines, alpha,beta- or beta,gamma-unsaturated ketones, can be selectively accessed. Both aromatic and aliphatic alkynes can be employed as coupling partners. The reaction conditions also tolerate a broad range of functional groups, including carboxylic esters, malonates, secondary amides, thioethers, and free alcohols. In addition, excellent E-selectivity was observed for the tetra-substituted alkene when forming the alpha,beta-unsaturated ketone products. The mechanism of this transformation was explored through control experiments, kinetic monitoring, synthesizing the rhodium-hydride intermediates and their reactions with alkynes, deuterium-labeling experiments, and identification of the resting states of the catalyst.; Cancer Prevention and Research Institute of Texas [R1118]; Welch Foundation [F-1781]; NSF [CAREER: CHE-1254935]; SCI(E); EI; ARTICLE; gbdong@cm.utexas.edu; 49; 15518-15527; 137
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/435552]
专题	工学院
推荐引用方式 GB/T 7714	Mo, Fanyang,Lim, Hee Nam,Dong, Guangbin. Bifunctional Ligand-Assisted Catalytic Ketone alpha-Alkenylation with Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2015.
APA	Mo, Fanyang,Lim, Hee Nam,&Dong, Guangbin.(2015).Bifunctional Ligand-Assisted Catalytic Ketone alpha-Alkenylation with Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY.
MLA	Mo, Fanyang,et al."Bifunctional Ligand-Assisted Catalytic Ketone alpha-Alkenylation with Internal Alkynes: Controlled Synthesis of Enones and Mechanistic Studies".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2015).