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Copper-Catalyzed Enantioselective Radical 1,4-Difunctionalization of 1,3-Enynes

Yuehua Zeng, Mong‐Feng Chiou, Xiaotao Zhu, Jie Cao, Daqi Lv, Wujun Jian, Yajun Li, Xinhao Zhang, Hongli Bao

2020Journal of the American Chemical Society181 citationsDOI

Abstract

pathway would complement previous methods and support expansion of the toolbox for the synthesis of asymmetric allenes. Herein, we report the first radical enantioselective allene formation via a group transfer pathway in the context of copper-catalyzed radical 1,4-difunctionalization of 1,3-enynes. This method addresses a longstanding unsolved problem in asymmetric radical chemistry, provides an important strategy for stereocontrol with free allenyl radicals, and offers a novel approach to the valuable, but previously inaccessible, chiral allenes. This work should shed light on asymmetric radical reactions and may lead to other enantioselective group transfer reactions.

Topics & Concepts

ChemistryEnantioselective synthesisAlleneCombinatorial chemistryElectrophileRadicalChirality (physics)Organic synthesisCatalysisStereochemistryOrganic chemistryChiral symmetry breakingQuarkPhysicsNambu–Jona-Lasinio modelQuantum mechanicsCatalytic C–H Functionalization MethodsRadical Photochemical ReactionsSulfur-Based Synthesis Techniques