Photocatalytic Ketyl Radical Initiated C ketyl −C sp2 /C sp3 Coupling on ZnIn 2 S 4
Photocatalytic Ketyl Radical Initiated C ketyl −C sp2 /C sp3 Coupling on ZnIn 2 S 4
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光催化羰基自由基引发的 C ketyl →C sp2 /C sp3 在 ZnIn 2 S 4 上的偶联
DOI：
10.1002/chem.202203785
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Sun, Yujie
中科院分区：
文献类型：
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作者：
Han, Chuang;Han, Guanqun;Habibur Rahman, Md;Mannodi‐Kanakkithodi, Arun;Sun, Yujie
利用酮基物种在可见光驱动下形成C-−-C键最近引起了越来越多的关注，因为它为合成复杂分子提供了一条直接的途径。然而，目前研究最多的均相光催化体系用于生成和利用酮基自由基，通常需要贵金属光敏剂(如 ，Ru和Ir)，这些光敏剂不仅成本高，而且可能被降解，从而给产物的分离和纯化带来了挑战。相比之下，易获得、廉价和可回收的半导体代表了一类有吸引力的替代光催化剂，但在光催化酮基自由基引发的C-−-C键形成方面的研究要少得多。本工作表明，在可见光照射下，通过分子内环化反应(Cketyl−Csp2)和分子间交叉偶联反应(Cketyl−Csp3)，可以在ZnIn2S4上利用酮基自由基生成包括取代色曼和叔醇在内的一系列重要的工业化学品。在计算研究的辅助下，开展了一系列实验研究，以揭示这两种酮基引发的C-−-C偶联反应的机理。
Visible‐light‐driven C−C bond formation utilizing ketyl radical (Cketyl) species has attracted increasing attention recently, as it provides a direct route for the synthesis of complex molecules. However, the most‐developed homogeneous photocatalytic systems for the generation and utilization of ketyl radicals usually entail noble metal‐based (e. g., Ru and Ir) photosensitizers, which suffer from not only high cost but also potential degradation and hence pose challenges in product separation and purification. In contrast, readily accessible, inexpensive, and recyclable semiconductors represent a class of attractive and alternative photocatalysts but remain much less explored for photocatalytic ketyl radical initiated C−C bond formation. This work demonstrates that a wide range of industrially important chemicals, including substituted chromanes and tertiary alcohols, can be produced on ZnIn2S4under visible light irradiation through intramolecular cyclization (Cketyl−Csp2) and intermolecular cross‐coupling (Cketyl−Csp3) reactions, respectively, using ketyl radicals. A suite of experimental studies aided by computational investigation were carried out to shed light on the mechanistic insights of these two types of ketyl radical initiated C−C coupling reactions on ZnIn2S4.