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Enantioselective S‐Alkylation of Sulfenamides With Copper‐Catalyzed Amino‐Radical‐Transfer Deboronation

Ke Wang, Yu Qi, Menghui Ding, Qi Tang, Xiaodong Shi, Xiaohan Ye

2026Angewandte Chemie International Edition6 citationsDOIOpen Access PDF

Abstract

ABSTRACT This work reports a copper‐catalyzed enantioselective S‐alkylation of sulfenamides enabled by an amino‐radical‐transfer deboronation pathway. Chiral sulfilimines are obtained in high yields (up to 95%) and enantioselectivities (up to 98% ee) under mild conditions. An isomerizable bis(oxazoline) ligand bearing a bridging CH 2 unit is identified as the key factor for both reactivity and stereoselectivity in the copper‐catalyzed radical‐relay coupling with sulfenamides. The method offers a general platform for accessing enantioenriched S(IV) architectures with aliphatic substituents and demonstrates strong potential for applications in medicinal chemistry.

Topics & Concepts

Enantioselective synthesisChemistryReactivity (psychology)StereochemistryStereoselectivityLigand (biochemistry)Combinatorial chemistryStereoisomerismOrganic chemistryBridging (networking)Coupling (piping)Catalytic C–H Functionalization MethodsRadical Photochemical ReactionsSulfur-Based Synthesis Techniques
Enantioselective S‐Alkylation of Sulfenamides With Copper‐Catalyzed Amino‐Radical‐Transfer Deboronation | Litcius