Ligand-Controlled Reactivity, Selectivity, and Mechanism of Cationic   Ruthenium-Catalyzed Hydrosilylations of Alkynes, Ketones, and Nitriles:   A Theoretical Study

doi:10.1021/jo501730n

CORC > 北京大学 > 化学与分子工程学院

	Ligand-Controlled Reactivity, Selectivity, and Mechanism of Cationic Ruthenium-Catalyzed Hydrosilylations of Alkynes, Ketones, and Nitriles: A Theoretical Study
	Yang, Yun-Fang ; Chung, Lung Wa ; Zhang, Xinhao ; Houk, K. N. ; Wu, Yun-Dong
刊名	journal of organic chemistry
	2014
关键词	TRANSITION-ELEMENTS INTERNAL ALKYNES METAL-COMPLEXES BOND HYDROSILATION ACTIVATION ORIGINS OLEFINS ENERGY
DOI	10.1021/jo501730n
英文摘要	Density functional theory calculations with the M06 functional have been performed on the reactivity, selectivity, and mechanism of hydrosilylations of alkynes, ketones, and nitriles catalyzed by cationic ruthenium complexes [CpRu(L)(MeCN)(2)](+), with L = (PPr3)-Pr-i or MeCN. The hydrosilylation of alkynes with L = (PPr3)-Pr-i involves an initial silyl migration mechanism to generate the anti-Markovnikov product, in contrast to the Markovnikov product obtained with L = MeCN. The bulky phosphine ligand directs the silyl group to migrate to C-beta of the alkyne. This explains the anti-Markovnikov selectivity of the catalyst with L = (PPr3)-Pr-i. By contrast, the silane additions to either ketone or nitrile proceed through an ionic S(N)2-Si outer-sphere mechanism, in which the substrate attacks the Si center. The (PPr3)-Pr-i ligand facilitates the activation of the Si-H bond to furnish a eta(2)-silane complex, whereas a eta(1)-silane complex is formed for the MeCN ligand. This property of the phosphine ligand enables the catalytic hydrosilylation of ketones and nitriles in addition to that of alkynes.; Chemistry, Organic; SCI(E); EI; PubMed; 5; ARTICLE; oscarchung@sustc.edu.cn; houk@chem.ucla.edu; wuyd@pkusz.edu.cn; 18; 8856-8864; 79
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/342266]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Yang, Yun-Fang,Chung, Lung Wa,Zhang, Xinhao,et al. Ligand-Controlled Reactivity, Selectivity, and Mechanism of Cationic Ruthenium-Catalyzed Hydrosilylations of Alkynes, Ketones, and Nitriles: A Theoretical Study[J]. journal of organic chemistry,2014.
APA	Yang, Yun-Fang,Chung, Lung Wa,Zhang, Xinhao,Houk, K. N.,&Wu, Yun-Dong.(2014).Ligand-Controlled Reactivity, Selectivity, and Mechanism of Cationic Ruthenium-Catalyzed Hydrosilylations of Alkynes, Ketones, and Nitriles: A Theoretical Study.journal of organic chemistry.
MLA	Yang, Yun-Fang,et al."Ligand-Controlled Reactivity, Selectivity, and Mechanism of Cationic Ruthenium-Catalyzed Hydrosilylations of Alkynes, Ketones, and Nitriles: A Theoretical Study".journal of organic chemistry (2014).