Visible Light-Driven Metal-Organic Framework-Mediated Activation and Utilization of CO 2 for the Thiocarboxylation of Olefins.

Visible light-mediated photoredox catalysis has emerged to be a fascinating approach for the activation of CO 2 and its subsequent fixation into valuable chemicals utilizing renewable and inexhaustible solar energy. Although great progress has been made in CO 2 photoreduction, visible light-assisted organic synthesis using CO 2 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 2 and thiols over a porous functionalized metal-organic framework (MOF), Fe-MIL-101-NH 2 , 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 2 interacts with the thiophenol-styrene adduct to facilitate the synthesis of β-thioacids in almost quantitative yields.