Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors

doi:10.1021/jacs.0c00078

	Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors
	Song, Bichao 4,5; Xie, Peipei 2; Li, Yingzi 3; Hao, Jiping 4; Wang, Lu 4; Chen, Xiangyang 3; Xu, Zhongliang 4,5; Quan, Haitian 6; Lou, Liguang 6; Xia, Yuanzhi 2
刊名	JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
	2020-06-03
卷号	142 期号:22 页码:9982-9992
ISSN号	0002-7863
DOI	10.1021/jacs.0c00078
通讯作者	Xia, Yuanzhi(xyz@wzu.edu.cn) ; Houk, K. N.(houk@chem.ucla.edu) ; Yang, Weibo(yweibo@simm.ac.cn)
英文摘要	The efficient and stereoselective synthesis of polysubstituted butadienes, especially the multifunctional butadienes, represents a great challenge in organic synthesis. Herein, we wish to report a distinctive Pd(0) carbene-initiated decarboxylative olefination approach that enables the direct coupling of diazo esters with vinylethylene carbonates (VECs), vinyl oxazolidinones, or vinyl benzoxazinones to afford alcohol-, amine-, or aniline-containing 1,3-dienes in moderate to high yields and with excellent stereoselectivity. This protocol features operational simplicity, mild reaction conditions, a broad substrate scope, and gram-scalability. Notably, a structurally unique allylic Pd(II) intermediate was isolated and characterized. DFT calculation and control experiments demonstrated that a rare Pd(0) carbene intermediate could be involved in this reaction. Moreover, the polysubstituted butadienes as novel building blocks were unprecedentedly assembled into macrocycles, which efficiently inhibited the P-glycoprotein and dramatically reversed multidrug resistance in cancer cells by 190-fold.
资助项目	100 talent program of Chinese Academy of Sciences ; NSFC[21702217] ; NSFC[21572163] ; NSFC[21873074] ; 1000-Youth Talents Plan ; National Science & Technology Major Project Key New Drug Creation and Manufacturing Program China[2018ZX09711002-006] ; Shanghai-Technology Innovation Action Plan[18JC1415300] ; U.S. National Science Foundation[CHE-1764328] ; Shanghai-Youth Talent
WOS关键词	VINYLETHYLENE CARBONATES ; NHC LIGANDS ; PALLADIUM ; ROUTE ; FUNCTIONALIZATION ; HYDROGENATION ; CYCLOADDITION ; CONSTRUCTION ; DIAZOESTERS ; COMPLEXES
WOS研究方向	Chemistry
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000538526500014
内容类型	期刊论文
源URL	[http://119.78.100.183/handle/2S10ELR8/291655]
专题	中国科学院上海药物研究所
通讯作者	Xia, Yuanzhi; Houk, K. N.; Yang, Weibo
作者单位	1.Univ Sci & Technol Liaoning, Educ Dept Liaoning Prov, Key Lab Funct Mat, Anshan 114051, Peoples R China 2.Wenzhou Univ, Coll Chem & Mat Engn, Wenzhou 325035, Peoples R China 3.Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA 4.Chinese Acad Sci, SIMM, Key Lab Receptor Res, Shanghai, Peoples R China 5.Univ Chinese Acad Sci, Beijing 100049, Peoples R China 6.Chinese Acad Sci, Shanghai Inst Mat Med, Shanghai 201203, Peoples R China
推荐引用方式 GB/T 7714	Song, Bichao,Xie, Peipei,Li, Yingzi,et al. Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2020,142(22):9982-9992.
APA	Song, Bichao.,Xie, Peipei.,Li, Yingzi.,Hao, Jiping.,Wang, Lu.,...&Yang, Weibo.(2020).Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors.JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,142(22),9982-9992.
MLA	Song, Bichao,et al."Pd-Catalyzed Decarboxylative Olefination: Stereoselective Synthesis of Polysubstituted Butadienes and Macrocyclic P-glycoprotein Inhibitors".JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 142.22(2020):9982-9992.