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Copper-Catalyzed Highly Efficient and Asymmetric Allylic C–H Oxidation of 3-Aryl-Substituted Terminal Alkenes

Ying Zhou, Pinhong Chen, Guosheng Liu

2025Journal of the American Chemical Society16 citationsDOI

Abstract

Asymmetric allylic C(sp 3 )–H oxidation of terminal alkenes provides a streamlined process for accessing allylic alcohols and their derivatives; however, it represents a long-standing challenge in the field for several decades. Herein, we disclosed a copper-catalyzed approach for the enantioselective allylic C(sp 3 )–H oxidation of terminal alkenes, facilitated by introducing a sterically bulky B 2 Im(C 6 F 5 ) 6 anion. Notably, a wide range of aryl-substituted terminal alkenes were used as limiting reagents, delivering various products with excellent enantioselectivity and regioselectivity (up to 99% ee, >20:1 b/l). Mechanistically, the bulky counteranion was found to be essential for achieving excellent enantioselective control and high catalytic efficiency.

Topics & Concepts

Allylic rearrangementChemistryEnantioselective synthesisRegioselectivityCatalysisArylSteric effectsReagentCopperCombinatorial chemistryLimitingMedicinal chemistryOrganic chemistryEngineeringAlkylMechanical engineeringCatalytic C–H Functionalization MethodsOxidative Organic Chemistry ReactionsSynthesis and Catalytic Reactions
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