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双催化中的绿色分子转化:使用多相光催化剂实现维生素 B 的光还原活化。

Green Molecular Transformation in Dual Catalysis: Photoredox Activation of Vitamin B Using Heterogeneous Photocatalyst.

机构信息

Department of Chemistry and Biochemistry, Graduate School of Engineering, Kyushu University, Nishi-ku, Motooka, Fukuoka, 744, 819-0395, Japan.

出版信息

Chempluschem. 2024 Jun;89(6):e202400041. doi: 10.1002/cplu.202400041. Epub 2024 Mar 12.

Abstract

This concept focuses on dual-catalysis using metal complexes and heterogeneous photocatalysts. Vitamin B derivatives are sophisticated metal complexes that facilitate enzymatic reactions in the biological systems. The B enzymes inspired reactions catalytically proceed in dual-catalyst systems of B derivatives and heterogeneous photocatalysts, such as titanium oxide (TiO) and metal-organic frameworks (MOFs), under light irradiation. The cobalt ions in B derivatives are effectively reduced by photoexcited photocatalysts, producing low-valent Co(I) species. The photoinduced nucleophilic Co(I) species react with an alkyl halide to form an organometallic complex with a Co-C bond. The Co-C bond dissociates during photolysis to generate alkyl radicals. Based on this mechanism, dual-catalysis effectively promotes various light-driven organic syntheses and light-driven dehalogenation reactions of toxic alkyl halides. The trends of the dual-catalyst system and recent progress in this field are discussed in this concept.

摘要

这一概念侧重于使用金属配合物和多相光催化剂的双催化。维生素 B 衍生物是复杂的金属配合物,可促进生物体系中的酶反应。受 B 酶启发的反应在 B 衍生物和多相光催化剂(如二氧化钛(TiO)和金属有机骨架(MOFs))的双催化剂体系中,在光照下催化进行。B 衍生物中的钴离子被光激发的光催化剂有效还原,生成低价态 Co(I)物种。光诱导亲核 Co(I)物种与烷基卤化物反应,形成具有 Co-C 键的有机金属络合物。在光解过程中,Co-C 键解离生成烷基自由基。基于这一机制,双催化有效地促进了各种光驱动的有机合成以及有毒烷基卤化物的光驱动脱卤反应。本综述讨论了双催化剂体系的发展趋势和该领域的最新进展。

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