Rhodium(I)-Catalyzed Intermolecular Aza-[4+3] Cycloaddition of Vinyl Aziridines and Dienes: Atom-Economical Synthesis of Enantiomerically Enriched Functionalized Azepines

Chao-Ze Zhu; Jian-Jun Feng; Junliang Zhang

doi:10.1002/anie.201609608

Rhodium(I)-Catalyzed Intermolecular Aza-[4+3] Cycloaddition of Vinyl Aziridines and Dienes: Atom-Economical Synthesis of Enantiomerically Enriched Functionalized Azepines

Angew Chem Int Ed Engl. 2017 Jan 24;56(5):1351-1355. doi: 10.1002/anie.201609608. Epub 2016 Dec 14.

Authors

Chao-Ze Zhu¹, Jian-Jun Feng¹, Junliang Zhang^{1

2}

Affiliations

¹ Shanghai Key Laboratory of Green Chemistry and Chemical, Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, 200062, P. R. China.
² State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, China.

PMID: 27966804
DOI: 10.1002/anie.201609608

Abstract

A new synthetic application of vinyl aziridines as N-containing three-atom components in a rhodium-catalyzed [4+3] cycloaddition reaction is described. The reaction proceeds well with various silyl dienol ethers and vinyl aziridines, and enables the efficient synthesis of highly functionalized azepines in an enantioselective manner with net inversion of absolute configuration. The salient features of the transformation include the use of readily available substrates, high selectivity, and mild reaction conditions, as well as the versatile functionalization of the products.

Keywords: [4+3] cycloaddition; chiral azepines; chirality transfer; dienes; vinyl aziridines.

Publication types

Research Support, Non-U.S. Gov't