Visible-Light-Mediated Difunctionalization of Alkynes: Synthesis of β-Substituted Vinylsulfones Using O- and S-Centered Nucleophiles

An inimitable illustration of a green-light-induced, regioselective difunctionalization of terminal alkynes has been disclosed using sodium arylsulfinates and carboxylic acids in the presence of eosin Y as the photocatalyst. The present methodology is further demonstrated by employing NH4SCN as an S-centered nucleophile instead of carboxylic acid. The mechanistic investigation reveals a radical-induced iodosulfonylation followed by a base-mediated nucleophilic substitution. The mechanism is supported by various studies, viz., radical-trapping experiment, fluorescence quenching, and CV studies. In this protocol, (Z)-beta-substituted vinylsulfones are obtained, exclusively covering a broad range of alkynes and nucleophiles, which are often unaddressed. The present strategy can tolerate structurally discrete substrates with steric bulk and different electronic properties, which provides a straightforward and practical pathway for the synthesis of highly functionalized (Z)-beta-substituted vinylsulfones. Herein, C-O and C-S bonds are assembled simultaneously with the concomitant introduction of important functional groups, viz., ester, thiocyanate, and sulfone.

Automated summary

This study presents a novel green-light-induced regioselective difunctionalization of terminal alkynes using sodium arylsulfinates, carboxylic acids or NH4SCN, and eosin Y as the photocatalyst. The mechanism involves a radical-induced iodosulfonylation followed by a base-mediated nucleophilic substitution. The methodology allows for the synthesis of highly functionalized (Z)-beta-substituted vinylsulfones with tolerance to structurally diverse substrates, providing a practical pathway for C-O and C-S bond assembly.