(493d) Visible Light Mediated Switchable Selectivity in C-O, C-C and C-S Bond Formation Induced By Disulfide

Meng, Q., Dalian University of Technology
Zhao, J., Dalian University of Technology
Chemists are beginning to turn their attention to the development of catalysts whose activity in a given chemical processes can be switched by an external stimulus. To achieve a mild, selectivity-controllable and general C-O, C-C and C-S bond formation, the facile selectivity-switchable functionalization of 1,3-dicarbonyl compounds represents an ideal protocol, yet a significant challenge. We thus focused on developing a bioinspired strategy. In this work, a visible light-mediated a-functionalization of 1,3- dicarbonyl compounds with switchable selectivity induced by disulfide is disclosed for the first time. Upon irradiation with visible light, the metal- and base-free α-hydroxylation and α-hydroxymethylation reactions proceeded smoothly through a disulfide-catalyzed oxidation with air under mild conditions and generated the desired products. The highly tunable selectivity between the hydroxylation (21 examples, up to 98% yield) and hydroxymethylation (20 examples, up to 97% yield) is controlled by simple changes in the stoichiometry of the styrene additive. In contrast, conducting the reaction in darkness prevented the S-S bond from being photoactivated, and the disulfides served as a sulfurization reagent and promoted the α-sulfenylation (15 examples, up to 95% yield). The reaction efficiencies of the hydroxylation and hydroxymethylation could be further improved by using a continuous-flow reactor. The combination of a continuous-flow strategy and enzyme-like switchable catalysts allowed the facile preparation of synthetically useful intermediates and products meanwhile providing a digital control and manipulation of chemical reaction paths.


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