Palladium-Catalyzed Meta-Selective C-H Bond Activation with a   Nitrile-Containing Template: Computational Study on Mechanism and   Origins of Selectivity

doi:10.1021/ja410485g

CORC > 北京大学 > 化学与分子工程学院

	Palladium-Catalyzed Meta-Selective C-H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity
	Yang, Yun-Fang ; Cheng, Gui-Juan ; Liu, Peng ; Leow, Dasheng ; Sun, Tian-Yu ; Chen, Ping ; Zhang, Xinhao ; Yu, Jin-Quan ; Wu, Yun-Dong ; Houk, K. N.
刊名	journal of the american chemical society
	2014
关键词	INTRAMOLECULAR ALKANE ARYLATION PROTON-ABSTRACTION MECHANISM AB-INITIO PSEUDOPOTENTIALS ELECTRON-DEFICIENT ARENES MOLECULAR-ORBITAL METHODS EFFECTIVE CORE POTENTIALS REMOTE FUNCTIONALIZATION DENSITY FUNCTIONALS TRANSITION-ELEMENTS POLARIZATION FUNCTIONS
DOI	10.1021/ja410485g
英文摘要	Density functional theory investigations have elucidated the mechanism and origins of meta-regioselectivity of Pd(II)-catalyzed C-H olefinations of toluene derivatives that employ a nitrile-containing template. The reaction proceeds through four major steps: C-H activation, alkene insertion, beta-hydride elimination, and reductive elimination. The C-H activation step, which proceeds via a concerted metalation-deprotonation (CMD) pathway, is found to be the rate- and regioselectivity-determining step. For the crucial C-H activation, four possible active catalytic species monomeric Pd(OAc)(2), dimeric Pd-2(OAc)(4), heterodimeric PdAg-(OAc)(3), and trimeric Pd-3(OAc)(6)-have been investigated. The computations indicated that the C-H activation with the nitrile-containing template occurs via a Pd Ag heterodimeric transition state. The nitrile directing group coordinates with Ag while the,Pd is placed adjacent to the meta-C-H bond in the transition state, leading to the observed high meta-selectivity. The Pd-2(OAc)(4) dimeric mechanism also leads to the meta-C-H activation product but with higher activation energies than the Pd Ag heterodimeric mechanism. The Pd monomeric and trimeric mechanisms require much higher activation free energies and are predicted to give ortho products. Structural and distortion energy analysis of the transition states revealed significant effects of distortions of the template on mechanism and regioselectivity, which provided hints for further developments of new templates.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000329586600058&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Multidisciplinary; SCI(E); EI; PubMed; 80; ARTICLE; yu200@scripps.edu; chydwu@ust.hk; houk@chem.ucla.edu; 1; 344-355; 136
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/189762]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Yang, Yun-Fang,Cheng, Gui-Juan,Liu, Peng,et al. Palladium-Catalyzed Meta-Selective C-H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity[J]. journal of the american chemical society,2014.
APA	Yang, Yun-Fang.,Cheng, Gui-Juan.,Liu, Peng.,Leow, Dasheng.,Sun, Tian-Yu.,...&Houk, K. N..(2014).Palladium-Catalyzed Meta-Selective C-H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity.journal of the american chemical society.
MLA	Yang, Yun-Fang,et al."Palladium-Catalyzed Meta-Selective C-H Bond Activation with a Nitrile-Containing Template: Computational Study on Mechanism and Origins of Selectivity".journal of the american chemical society (2014).