On the Mechanism of the Palladium Catalyzed Intramolecular   Pauson-Khand-Type Reaction

doi:10.1021/jo900919v

CORC > 北京大学 > 化学与分子工程学院

	On the Mechanism of the Palladium Catalyzed Intramolecular Pauson-Khand-Type Reaction
	Lan, Yu ; Deng, Lujiang ; Liu, Jing ; Wang, Can ; Wiest, Olaf ; Yang, Zhen ; Wu, Yun-Dong
刊名	journal of organic chemistry
	2009
关键词	BETA-HYDRIDE ELIMINATION BICYCLIC CYCLOPENTENONES ORGANOCOBALT COMPLEXES COUPLING REACTIONS ENYNES CYCLIZATION CYCLOADDITION DERIVATIVES MODEL 1,6-ENYNES
DOI	10.1021/jo900919v
英文摘要	Density functional theory calculations and experimental studies have been carried out on the intramolecular Pauson-Khand-Type reaction mediated by a PdCl2-thiourea catalyst, which proceeds under mild reaction conditions and provides a useful alternative to traditional Pauson-Khand reactions. The classical mechanism of the Pauson-Khand reaction involving the alkyne/alkene C-C bond formation as the key step has been found to be energetically unfavorable and is not in line with the experimental observations. A novel reaction mechanism has been proposed for the reaction. The first step involves the cis-halometalation of the alkyne, followed by sequential alkene and carbonyl insertion. The rate-determining fourth step is an intramolecular C-Cl oxidative addition, leading to a Pd-IV intermediate, A C-C bond formation by reductive elimination completes the reaction. The mechanism is in agreement with the key experimental observations including (I) the need of a chloride for catalytic activity and the absence of catalysis with Pd(OAC)(2) alone; (2) the rate acceleration by the addition of LiCl; both with PdCl2 and Pd(OAc)(2) catalysts; and (3) the preferred formation of the traits diastereomer in substituted cases. The cis halometalation and the formation and stability of the Pd-IV intermediate is studied in detail and provides general insights into these novel steps.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000268139700017&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Organic; SCI(E); EI; PubMed; 30; REVIEW; 14; 5049-5058; 74
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/197239]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Lan, Yu,Deng, Lujiang,Liu, Jing,et al. On the Mechanism of the Palladium Catalyzed Intramolecular Pauson-Khand-Type Reaction[J]. journal of organic chemistry,2009.
APA	Lan, Yu.,Deng, Lujiang.,Liu, Jing.,Wang, Can.,Wiest, Olaf.,...&Wu, Yun-Dong.(2009).On the Mechanism of the Palladium Catalyzed Intramolecular Pauson-Khand-Type Reaction.journal of organic chemistry.
MLA	Lan, Yu,et al."On the Mechanism of the Palladium Catalyzed Intramolecular Pauson-Khand-Type Reaction".journal of organic chemistry (2009).