Revealing a Second Transmetalation Step in the Negishi Coupling and Its   Competition with Reductive Elimination: Improvement in the   Interpretation of the Mechanism of Biaryl Syntheses

doi:10.1021/ja903277d

CORC > 北京大学 > 化学与分子工程学院

	Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses
	Liu, Qiang ; Lan, Yu ; Liu, Jing ; Li, Gang ; Wu, Yun-Dong ; Lei, Aiwen
刊名	journal of the american chemical society
	2009
关键词	CARBON BOND FORMATION OXIDATIVE ADDITION ARYL HALIDES PALLADIUM(0) COMPLEXES STILLE REACTION ARYLPALLADIUM COMPLEXES ORGANOMETAL COMPOUNDS TRANSITION-METALS ORGANIC GROUPS EXCHANGE
DOI	10.1021/ja903277d
英文摘要	This paper presents an experimental and theoretical investigation of the Pd-catalyzed Negishi coupling reaction and reveals a novel second transmetalation reaction between an Ar(1)-Pd-Ar(2) species and the organozinc reagent Ar(2)-ZnX. Understanding of this second step reveals how homocoupling and dehalogenation products are formed. Thus, the second transmetalation generates Ar(2)PdAr(2) and Ar(1)ZnCl, which upon reductive elimination and hydrolysis, respectively, give the homocoupling product Ar(2)-Ar(2) and the dehalogenation product Ar(1)H. The ratio of the cross-coupling product Ar(1)-Ar(2) and the homocoupling product Ar(2)-Ar(2) is determined by competition between the second transmetalation and reductive elimination steps. This mechanism is further supported by density functional theoretical calculations. Calculations on a series of reactions suggest a strategy in controlling the selectivity of cross-coupling and homocoupling pathways, which we have experimentally verified.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000268395000068&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Multidisciplinary; SCI(E); EI; 92; ARTICLE; 29; 10201-10210; 131
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/246794]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Liu, Qiang,Lan, Yu,Liu, Jing,et al. Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses[J]. journal of the american chemical society,2009.
APA	Liu, Qiang,Lan, Yu,Liu, Jing,Li, Gang,Wu, Yun-Dong,&Lei, Aiwen.(2009).Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses.journal of the american chemical society.
MLA	Liu, Qiang,et al."Revealing a Second Transmetalation Step in the Negishi Coupling and Its Competition with Reductive Elimination: Improvement in the Interpretation of the Mechanism of Biaryl Syntheses".journal of the american chemical society (2009).