Palladium-Catalyzed Highly Chemo- and Stereoselective Bisthiolation of Terminal Alkynes with Allyl Phenyl Sulfides via C–S Bond Cleavage

Abstract

A facile and general method for palladium-catalyzed stereoselective bisthiolation of terminal alkynes with allyl phenyl sulfides has been developed. The scope and versatility of the reaction have been demonstrated, and a broad range of substrates bearing electron-donating and -withdrawing groups on the aromatic rings were all compatible with this reaction, providing the desired (Z)-1,2-dithio-1-alkenes in moderate to good yields. Preliminary mechanistic studies demonstrated that the sulfur source of the desired products may be successively incorporated into alkynes via C−S bond cleavage of two molecules of allyl phenyl sulfides and ruled out the possibility of vinyl sulfides, alkynyl sulfides, and disulfide intermediates being involved in this reaction.

Recent advances in the dichalcogenation reactions of unsaturated compounds via double functionalization

“…In 2022, Zhang and coworkers described a novel protocol for the synthesis of ( Z )-1,2-dithio-1-alkenes via Pd-catalyzed, MeOH-facilitated stereoselective bis-thiolation of terminal alkynes 19a with allyl phenyl sulfides 19b , wherein the two sulfur-containing moieties are successively incorporated through C–S bond cleavage of two molecules of allyl phenyl sulfides (Scheme 19). 34 A variety of aryl, heteroaryl and alkyl terminal alkynes, including those bearing terminal –NH 2 and –OH groups, were highly compatible with this protocol. Moreover, the bis-thiolation proceeded smoothly even with sterically bulkier ortho -substituted allyl phenyl sulfides or naphthyl-substituted allyl sulfide.…”

Palladium-Catalyzed Thiocarbonylation of Aryl Iodides with S-Aryl Thioformates via Thioester Transfer

“…However, the corresponding thioesterification of aryl halides via thioester group transfer of S -aryl thioformates has never been investigated. To realize this transformation and in keeping with our research for the synthesis of thioethers and thioester compounds, herein, we report a novel and practical method for the synthesis of thioesters utilizing S -aryl thioformates as thioester sources (Scheme g).…”