Desulfurdioxidative N-N Coupling of N-Arylhydroxylamines and N-Sulfinylanilines: Reaction Development and Mechanism

Linwei Li; Yi Zhou; Zhenguo Xi; Zhaoquan Guo; Ji-Cheng Duan; Zhi-Xiang Yu; Hongyin Gao

doi:10.1002/anie.202406478

Desulfurdioxidative N-N Coupling of N-Arylhydroxylamines and N-Sulfinylanilines: Reaction Development and Mechanism

Angew Chem Int Ed Engl. 2024 Apr 18:e202406478. doi: 10.1002/anie.202406478. Online ahead of print.

Authors

Linwei Li¹, Yi Zhou², Zhenguo Xi¹, Zhaoquan Guo¹, Ji-Cheng Duan², Zhi-Xiang Yu², Hongyin Gao³

Affiliations

¹ Shandong University, School of Chemistry and Chemical Engineering, CHINA.
² Peking University, Beijing National Laboratory for Molecular Sciences (BNLMS) Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, CHINA.
³ Shandong University, School of Chemistry and Chemical Engineering, 27 South Shanda Road, 250100, Ji'nan, CHINA.

PMID: 38637953
DOI: 10.1002/anie.202406478

Abstract

A highly efficient and chemoselective approach for the divergent assembling of unsymmetrical hydrazines through an unprecedented intermolecular desulfurdioxidative N-N coupling is developed. This metal free protocol employs readily accessible N-arylhydroxylamines and N-sulfinylanilines to provide highly valuable hydrazine products with good yields and excellent functional group tolerance under simple conditions. Computational studies suggest that the in situ generated O-sulfenylated arylhydroxylamine intermediate undergoes a retro-[2π+2σ] cycloaddition via a stepwise diradical mechanism to form the N-N bond and release SO2.

Keywords: N,N'-diaryl hydrazines; N-N coupling; N-arylhydroxylamines; N-sulfinylanilines; retro-[2π+2σ] cycloaddition.