Access to N-Substituted 2-Pyridones by Catalytic Intermolecular Dearomatization and 1,4-Acyl Transfer

Guangyang Xu; Ping Chen; Pei Liu; Shengbiao Tang; Xinhao Zhang; Jiangtao Sun

doi:10.1002/anie.201812937

Access to N-Substituted 2-Pyridones by Catalytic Intermolecular Dearomatization and 1,4-Acyl Transfer

Angew Chem Int Ed Engl. 2019 Feb 11;58(7):1980-1984. doi: 10.1002/anie.201812937. Epub 2018 Dec 27.

Authors

Guangyang Xu¹, Ping Chen², Pei Liu¹, Shengbiao Tang¹, Xinhao Zhang², Jiangtao Sun¹

Affiliations

¹ Jiangsu Key Laboratory of Advanced Catalytic Materials & Technology, School of Petrochemical Engineering, Changzhou University, 1 Gehu Road, 213164, Changzhou, China.
² Lab of Computational Chemistry and Drug Design, State Key Laboratory of Chemical Oncogeomics, Peking University Shenzhen Graduate School, Shenzhen, 518055, China.

PMID: 30516877
DOI: 10.1002/anie.201812937

Abstract

A novel rhodium-catalyzed dearomatization of O-substituted pyridines to access N-substituted 2-pyridones has been developed. A computational study suggests a mechanism involving the formation of a pyridinium ylide followed by an unprecedented 1,4-acyl migratory rearrangement from O to C. Furthermore, the chiral dirhodium complexes serve as the catalyst for the asymmetric transformation with excellent enantioselective control. DFT calculations indicate the chirality is transferred from axial chirality to the central stereogenic centre. The stronger π-π interaction and CH-π interaction account for the high enantioselectivity.

Keywords: asymmetric catalysis; carbenes; dearomatization; diazo compounds; rearrangement.

Abstract

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