Total Synthesis of (+)-Asteriscanolide: Further Exploration of the   Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO

doi:10.1002/asia.201100805

CORC > 北京大学 > 化学与分子工程学院

	Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO
	Liang, Yong ; Jiang, Xing ; Fu, Xu-Fei ; Ye, Siyu ; Wang, Tao ; Yuan, Jie ; Wang, Yuanyuan ; Yu, Zhi-Xiang
刊名	chemistry an asian journal
	2012
关键词	annulation cycloaddition radical reactions rhodium total synthesis RING-CLOSING METATHESIS HIGHLY ENANTIOSELECTIVE ALKYNYLATION CATALYZED 5+2 CYCLOADDITIONS CROSS-COUPLING REACTIONS (-)-PSEUDOLARIC ACID-B MEDIUM-SIZED RINGS GRIGNARD-REAGENTS CONCISE SYNTHESIS KETO ESTER CONSTRUCTION
DOI	10.1002/asia.201100805
英文摘要	The total synthesis of (+)-asteriscanolide is reported. The synthetic route features two key reactions: 1) the rhodium(I)-catalyzed [(5+2)+1] cycloaddition of a chiral ene-vinylcyclopropane (ene-VCP) substrate to construct the [6.3.0] carbocyclic core with excellent asymmetric induction, and 2) an alkoxycarbonyl-radical cyclization that builds the bridging butyrolactone ring with high efficiency. Other features of this synthetic route include the catalytic asymmetric alkynylation of an aldehyde to synthesize the chiral ene-VCP substrate, a highly regioselective conversion of the [(5+2)+1] cycloadduct into its enol triflate, and the inversion of the insideoutside tricycle to the outsideoutside structure by an ester-reduction/elimination to enol-ether/hydrogenation procedure. In addition, density functional theory (DFT) rationalization of the chiral induction of the [(5+2)+1] reaction and the diastereoselectivity of the radical annulation has been presented. Equally important is that we have also developed other routes to synthesize asteriscanolide using the rhodium(I)-catalyzed [(5+2)+1] cycloaddition as the key step. Even though these routes failed to achieve the total synthesis, these experiments gave further useful information about the scope of the [(5+2)+1] reaction and paved the way for its future application in synthesis.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000300871500020&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Multidisciplinary; SCI(E); PubMed; 24; ARTICLE; 3; 593-604; 7
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/191909]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Liang, Yong,Jiang, Xing,Fu, Xu-Fei,et al. Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO[J]. chemistry an asian journal,2012.
APA	Liang, Yong.,Jiang, Xing.,Fu, Xu-Fei.,Ye, Siyu.,Wang, Tao.,...&Yu, Zhi-Xiang.(2012).Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO.chemistry an asian journal.
MLA	Liang, Yong,et al."Total Synthesis of (+)-Asteriscanolide: Further Exploration of the Rhodium(I)-Catalyzed [(5+2)+1] Reaction of Ene-Vinylcyclopropanes and CO".chemistry an asian journal (2012).