Palladium-catalyzed regio- and enantioselective migratory allylic C(sp(3))-H functionalization

doi:10.1038/s41467-021-25978-6

	Palladium-catalyzed regio- and enantioselective migratory allylic C(sp(3))-H functionalization
	Chen, Ye-Wei1,2 ; Liu, Yang 1; Lu, Han-Yu 1,2; Lin, Guo-Qiang1,2 ; He, Zhi-Tao 1
	2021-09-24
发表期刊	NATURE COMMUNICATIONS (IF:14.7[JCR-2023],16.1[5-Year])
EISSN	2041-1723
卷号	12 期号:1
DOI	10.1038/s41467-021-25978-6
摘要	Transition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp(3))-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp(3))-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pK(a) values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process. Alkene isomerizations and asymmetric C-H functionalizations have been independently studied, but their combination in one protocol is uncommon. Here the authors show a palladium-catalyzed method to iteratively walk a terminal alkene along a carbon chain to a position next to styrenes where a soft nucleophile is added asymmetrically.
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收录类别	SCIE
语种	英语
WOS研究方向	Science & Technology - Other Topics
WOS类目	Multidisciplinary Sciences
WOS记录号	WOS:000698984500021
出版者	NATURE PORTFOLIO
原始文献类型	Article
引用统计	正在获取...
文献类型	期刊论文
条目标识符	https://kms.shanghaitech.edu.cn/handle/2MSLDSTB/128321
专题	物质科学与技术学院_硕士生物质科学与技术学院_特聘教授组_林国强组
通讯作者	Lin, Guo-Qiang; He, Zhi-Tao
作者单位	1.Univ Chinese Acad Sci, Shanghai Inst Organ Chem, Ctr Excellence Mol Synth, CAS Key Lab Synthet Chem Nat Subst, Shanghai, Peoples R China; 2.ShanghaiTech Univ, Sch Phys Sci & Technol, Shanghai, Peoples R China
第一作者单位	物质科学与技术学院
通讯作者单位	物质科学与技术学院
推荐引用方式 GB/T 7714	Chen, Ye-Wei,Liu, Yang,Lu, Han-Yu,et al. Palladium-catalyzed regio- and enantioselective migratory allylic C(sp(3))-H functionalization[J]. NATURE COMMUNICATIONS,2021,12(1).
APA	Chen, Ye-Wei,Liu, Yang,Lu, Han-Yu,Lin, Guo-Qiang,&He, Zhi-Tao.(2021).Palladium-catalyzed regio- and enantioselective migratory allylic C(sp(3))-H functionalization.NATURE COMMUNICATIONS,12(1).
MLA	Chen, Ye-Wei,et al."Palladium-catalyzed regio- and enantioselective migratory allylic C(sp(3))-H functionalization".NATURE COMMUNICATIONS 12.1(2021).