Stereospecific Aminative Cyclizations Triggered by Intermolecular Aza-Prilezhaev Alkene Aziridination

Matthew J S Smith; Wenbin Tu; Craig M Robertson; John F Bower

doi:10.1002/anie.202312797

Stereospecific Aminative Cyclizations Triggered by Intermolecular Aza-Prilezhaev Alkene Aziridination

Angew Chem Int Ed Engl. 2023 Nov 27;62(48):e202312797. doi: 10.1002/anie.202312797. Epub 2023 Oct 27.

Authors

Matthew J S Smith¹, Wenbin Tu^{1

2}, Craig M Robertson¹, John F Bower¹

Affiliations

¹ Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK.
² School of Chemistry, University of Bristol, Cantock's Close, Bristol, BS8 1TS, UK.

PMID: 37846756
DOI: 10.1002/anie.202312797

Abstract

Under acidic reaction conditions (TFA), deprotection of BocNR(OSO₂ R) reagents triggers intermolecular aminative cyclizations of alkenes equipped with pendant nucleophiles. The processes are predicated on a sequence of stereospecific intermolecular aza-Prilezhaev aziridination followed by stereospecific S_N 2-like opening by the pendant nucleophile. The method offers broad scope with respect to the nucleophile (N-, O- or C-based), alkene and cyclization mode, allowing the installation of two contiguous stereocenters under operationally simple conditions.

Keywords: Amination; Aza-Prilezhaev; Aziridine; Carbocyclization; Heterocyclization.

Grants and funding

China Scholarship Council