Visible Light-Driven Metal-Organic Framework-Mediated Activation and Utilization of CO for the Thiocarboxylation of Olefins.

Visible light-mediated photoredox catalysis has emerged to be a fascinating approach for the activation of CO and its subsequent fixation into valuable chemicals utilizing renewable and inexhaustible solar energy. Although great progress has been made in CO photoreduction, visible light-assisted organic synthesis using CO as a reactive substrate is rarely explored. Herein, we report an efficient, facile, and economically viable photoredox-mediated approach for the synthesis of important β-thioacids via carboxylation of olefins with CO and thiols over a porous functionalized metal-organic framework (MOF), Fe-MIL-101-NH, as a photocatalyst under ambient conditions. This multicomponent reaction offers wide substrate scope, mild reaction conditions, easy work-up, cost-effective and reusable photocatalysts, and higher product selectivity. Computational studies suggested that CO interacts with the thiophenol-styrene adduct to facilitate the synthesis of β-thioacids in almost quantitative yields.