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近年来,铜催化剂在可见光介导的烯烃和炔烃功能化方面取得了进展。

Recent advances in visible-light-mediated functionalization of olefins and alkynes using copper catalysts.

机构信息

Department of Chemistry, Sardar Vallabhbhai National Institute of Technology, Surat, Gujarat-395 007, India.

出版信息

Chem Commun (Camb). 2022 Jul 14;58(57):7850-7873. doi: 10.1039/d2cc01611g.

Abstract

Over the past decade, visible-light photoredox catalysis has blossomed as a powerful strategy and offers a discrete activation mode complementary to thermal controlled reactions. Visible-light-mediated photoredox catalysis also offers exciting opportunities to achieve challenging carbon-carbon and carbon-heteroatom bond formations with excellent chemo-, regio-, or stereoselectivity under mild and ecologically benign conditions. The greater part of photoredox reactions depends on heavy metals like ruthenium(II) or iridium(III) based complexes as photoredox catalysts owing to their strong absorption, long-lived excited-state lifetimes and high oxidation or redox potentials. However, these transition metal complexes are expensive and pose severe drawbacks with respect to large scale application and sustainability. Organic dyes are also commonly used as a low-cost alternative to Ru- or Ir-based complexes. However, they have inferior photostability. Thus, further development of alternative photocatalysts based on copper salts or copper complexes is widely investigated because of their economic and environmental benefits. In recent years, visible-light-mediated direct functionalization of olefins or alkynes to afford a diverse range of organic compounds has received extensive interest from synthetic chemists due to their easy availability and reactivity towards a large number of reactants. In this review, we have highlighted the most recent significant advances that have been made in the use of copper-based photocatalysts for the functionalization of olefins and alkynes with an emphasis on substrate scope, limitations, mechanistic understanding and applications of these reactions. This review covers the literature from 2015 to 2021.

摘要

在过去的十年中,可见光光氧化还原催化作为一种强大的策略蓬勃发展,提供了一种与热控反应互补的离散激活模式。可见光介导的光氧化还原催化也为实现具有优异的化学选择性、区域选择性或立体选择性的挑战性碳-碳和碳-杂原子键形成提供了令人兴奋的机会,在温和且生态良性的条件下进行。由于其强吸收、长寿命激发态寿命和高氧化或还原电位,大多数光氧化还原反应都依赖于钌(II)或铱(III)基配合物等重金属作为光氧化还原催化剂。然而,这些过渡金属配合物昂贵,并且在大规模应用和可持续性方面存在严重缺陷。有机染料也常用于替代 Ru 或 Ir 基配合物作为低成本替代品。然而,它们的光稳定性较差。因此,基于铜盐或铜配合物的替代光催化剂的进一步开发得到了广泛的研究,因为它们具有经济和环境效益。近年来,由于烯烃或炔烃的易得性和对大量反应物的反应性,可见光介导的烯烃或炔烃的直接官能化得到了合成化学家的广泛关注,以制备各种有机化合物。在这篇综述中,我们重点介绍了最近在使用铜基光催化剂对烯烃和炔烃进行官能化方面取得的重大进展,强调了这些反应的底物范围、局限性、机理理解和应用。本综述涵盖了 2015 年至 2021 年的文献。

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