Related Experiment Video
Updated: Jun 30, 2026

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Electrophilic alkene sulfenylation with sulfinate esters
Fei Xu1, Xuexin Han1, Jinyun Li1
1Department of Organic Chemistry, College of Science, Beijing University of Chemical Technology, Beijing 100029, P. R. China. dhg@mail.buct.edu.cn.
None:
An electrophilic alkene sulfenylation using sulfinate esters as readily available sulfur sources has been developed under mild HI activation. Terminal and 1,2-disubstituted alkenes, including cyclic substrates, predominantly undergo electrophilic addition to afford β-alkoxysulfides with high regio- and stereoselectivity. In contrast, 1,1-diarylethenes favor electrophilic substitution to give alkenyl sulfides selectively. Control experiments and Hammett analyses reveal that sulfinate esters serve as precursors to sulfur(II) electrophiles and that episulfonium ion formation constitutes the rate-determining step. These findings establish a systematic mechanistic framework for substrate-dependent divergence between electrophilic addition and substitution pathways.
Related Concept Videos
Preparation and Reactions of Sulfides
α-Alkylation of Ketones via Enolate Ions
Alkylation of β-Ketoester Enolates: Acetoacetic Ester Synthesis
Electrophilic Aromatic Substitution: Sulfonation of Benzene
α-Hydroxy Ketones via Reductive Coupling of Esters: Acyloin Condensation Overview
Acid Halides to Esters: Alcoholysis
