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Copper‐Catalyzed Asymmetric Coupling of Allenyl Radicals with Terminal Alkynes to Access Tetrasubstituted Allenes
Author(s) -
Dong XiaoYang,
Zhan TianYa,
Jiang ShengPeng,
Liu XiaoDong,
Ye Liu,
Li ZhongLiang,
Gu QiangShuai,
Liu XinYuan
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202013022
Subject(s) - radical , chirality (physics) , aryl , chemistry , catalysis , combinatorial chemistry , functional group , alkyl , axial chirality , enantioselective synthesis , photochemistry , organic chemistry , physics , chiral symmetry , quantum mechanics , nambu–jona lasinio model , quark , polymer
Abstract In contrast to the wealth of asymmetric transformations for generating central chirality from alkyl radicals, the enantiocontrol over the allenyl radicals for forging axial chirality represents an uncharted domain. The challenge arises from the unique elongated linear configuration of the allenyl radicals that necessitates the stereo‐differentiation of remote motifs away from the radical reaction site. We herein describe a copper‐catalyzed asymmetric radical 1,4‐carboalkynylation of 1,3‐enynes via the coupling of allenyl radicals with terminal alkynes, providing diverse synthetically challenging tetrasubstituted chiral allenes. A chiral N,N,P‐ligand is crucial for both the reaction initiation and the enantiocontrol over the highly reactive allenyl radicals. The reaction features a broad substrate scope, covering a variety of (hetero)aryl and alkyl alkynes and 1,3‐enynes as well as radical precursors with excellent functional group tolerance.