Structure-reactivity analysis of novel hypervalent iodine reagents in S-vinylation of thiols

Sayad Doobary; Ester Maria Di Tommaso; Alexandru Postole; A Ken Inge; Berit Olofsson

doi:10.3389/fchem.2024.1376948

Structure-reactivity analysis of novel hypervalent iodine reagents in S-vinylation of thiols

Front Chem. 2024 Feb 29:12:1376948. doi: 10.3389/fchem.2024.1376948. eCollection 2024.

Authors

Sayad Doobary¹, Ester Maria Di Tommaso¹, Alexandru Postole¹, A Ken Inge², Berit Olofsson¹

Affiliations

¹ Department of Organic Chemistry, Stockholm University, Stockholm, Sweden.
² Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, Sweden.

Abstract

The transition-metal free S-vinylation of thiophenols by vinylbenziodoxolones (VBX) constituted an important step forward in hypervalent iodine-mediated vinylations, highlighting the difference to vinyliodonium salts and that the reaction outcome was influenced by the substitution pattern of the benziodoxolone core. In this study, we report several new classes of hypervalent iodine vinylation reagents; vinylbenziodazolones, vinylbenziodoxolonimine and vinyliodoxathiole dioxides. Their synthesis, structural and electronic properties are described and correlated to the S-vinylation outcome, shedding light on some interesting facets of these reagents.

Keywords: VBX; X-ray crystallography; alkenes; benziodoxolones; hypervalency; reduction potential; structure-reactivity analysis.

Grants and funding

The author(s) declare financial support was received for the research, authorship, and/or publication of this article. Carl Trygger Foundation (20:316), the Swedish Research Council (2019-04232) and the Swedish Foundation for Strategic Research (SSF) are kindly acknowledged for financial support.