光催化
硫黄
吖啶
化学
组合化学
光化学
有机化学
催化作用
作者
Arka Porey,Seth Fremin,Sachchida Nand,Ramon Trevino,William Hughes,Shree Krishna Dhakal,Việt Dũng Nguyễn,Samuel G. Greco,Hadi D. Arman,Oleg V. Larionov
标识
DOI:10.26434/chemrxiv-2023-7wx16-v2
摘要
Development of photocatalytic systems that facilitate mechanistically different steps in complex catalytic manifolds by distinct activation modes can enable previously inaccessible synthetic transformations. However, multimodal photocatalytic systems remain understudied, impeding their implementation in catalytic methodology. We report herein a photocatalytic access to thiols that directly merges the structural diversity of carboxylic acids with the ready availability of elemental sulfur without substrate preactivation. The photocatalytic transformation provides a direct radical-mediated segue to one of the most biologically important and synthetically versatile organosulfur functionalities, whose synthetic accessibility remains largely dominated by two-electron-mediated processes based on toxic and uneconomical reagents and precursors. The two-phase radical process is facilitated by a multimodal catalytic reactivity of acridine photocatalysis that enables both the singlet excited state PCET-mediated decarboxylative carbon–sulfur bond formation and the previously unknown radical reductive disulfur bond cleavage by a photoinduced HAT process in the silane–triplet acridine system. The study points to a significant potential of multimodal photocatalytic systems in providing new directions to previously inaccessible transformations.
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