Trisulfur-Radical-Anion-Triggered C(sp2)-H Amination of Electron-Deficient Alkenes

Khang X Nguyen; Phuc H Pham; Thao T Nguyen; Chou-Hsun Yang; Hoai T B Pham; Tung T Nguyen; Haobin Wang; Nam T S Phan

doi:10.1021/acs.orglett.0c03846

Trisulfur-Radical-Anion-Triggered C(sp²)-H Amination of Electron-Deficient Alkenes

Org Lett. 2020 Dec 18;22(24):9751-9756. doi: 10.1021/acs.orglett.0c03846. Epub 2020 Dec 1.

Authors

Khang X Nguyen^{1

2}, Phuc H Pham^{1

2}, Thao T Nguyen^{1

2

3}, Chou-Hsun Yang⁴, Hoai T B Pham^{1

2

4}, Tung T Nguyen^{1

2}, Haobin Wang⁴, Nam T S Phan^{1

2}

Affiliations

¹ Faculty of Chemical Engineering, Ho Chi Minh City University of Technology (HCMUT), 268 Ly Thuong Kiet, District 10, Ho Chi Minh City, Vietnam.
² Vietnam National University Ho Chi Minh City, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Vietnam.
³ Tra Vinh University, 126 Nguyen Thien Thanh, Ward 5, Tra Vinh City, Tra Vinh Province, Vietnam.
⁴ Department of Chemistry, University of Colorado Denver, Denver, Colorado 80204, United States.

PMID: 33261315
DOI: 10.1021/acs.orglett.0c03846

Abstract

A trisulfur-radical-anion (S₃̇^-)-triggered C(sp²)-H amination of α,β-unsaturated carbonyl derivatives with simple amines has been demonstrated. This protocol provides convenient access to a variety of synthetically valuable N-unprotected and secondary β-enaminones with absolute Z selectivity and tertiary β-enaminones with E selectivity. Mechanistic probe and electronic structure theory calculations suggest that S₃̇^- initiates the nucleophilic attacks via a thiirane intermediate.