Catalytic Enantioselective Intramolecular Aza‐Michael Addition to α,β‐Unsaturated Esters

E Evan G. W. Rutter (Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK) C Cameron J. MacRae (Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK) H Haoran Xiong (Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK) D Daniel Rozsar (Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK) K Katherine F. P. Clarke (Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK) D Darren J. Dixon

Abstract

ABSTRACT A bifunctional iminophosphorane (BIMP)‐catalyzed enantioselective intramolecular aza‐Michael reaction of sulfonamides to tethered α,β‐unsaturated esters is described. Reactivity toward traditionally challenging ester Michael acceptors is achieved through careful catalyst design, enabling the synthesis of enantioenriched pyrrolidines, piperidines, and indoline derivatives in excellent yields (up to 99%) and enantiomeric ratios (up to 97.5:2.5 er) under operationally simple conditions. The broad reaction scope demonstrates excellent tolerance to variation in the sulfonamide group, the Michael acceptor, and substituents on the tether in between. Furthermore, the synthetic utility of the method is highlighted by gram‐scale reactions at reduced catalyst loadings and by downstream derivatization of multiple enantiopure products.

Article Details

Volume / Issue Vol. 65, Issue 30
Published July 20, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (6)

E

Evan G. W. Rutter

Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK

C

Cameron J. MacRae

Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK

H

Haoran Xiong

Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK

D

Daniel Rozsar

Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK

K

Katherine F. P. Clarke

Department of Chemistry Chemistry Research Laboratory University of Oxford Oxford UK

D

Darren J. Dixon