Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis.

Chiral Photocatalyst Structures in Asymmetric Photochemical Synthesis.
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DOI:
10.1021/acs.chemrev.1c00467
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发表时间:
2022-01-26
期刊:
影响因子:
62.1
通讯作者:
Yoon TP
Yoon TP
中科院分区:
化学1区
文献类型:
--
作者:
Genzink MJ;Kidd JB;Swords WB;Yoon TP

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不对称催化是当代合成有机化学的一个重要研究课题。然而,高对映选择性光化学反应的一般策略的发现是一个相对较新的发展,因此可以以立体控制的方式进行的各种光反应受到一定的限制。光生反应性中间体的短寿命和高反应性特征使不对称异构化复杂化;可以为这些中间体提供有效的对映体分化环境同时最小化不受控制的外消旋背景过程的参与的催化剂结构的设计已被证明是该领域进展的关键挑战。本文综述了近年来用于溶液相不对称光化学的手性催化剂结构,包括手性有机敏化剂、无机发色团和可溶性大分子。虽然这些光催化剂中的一些来自于对基态和光化学转化都有效的特权催化剂结构,但其他的是光催化剂特有的结构设计,并提供了对高效立体控制光催化剂所需逻辑的深入了解。
Asymmetric catalysis is a major theme of research in contemporary synthetic organic chemistry. The discovery of general strategies for highly enantioselective photochemical reactions, however, has been a relatively recent development, and the variety of photoreactions that can be conducted in a stereocontrolled manner is consequently somewhat limited. Asymmetric photocatalysis is complicated by the short lifetimes and high reactivities characteristic of photogenerated reactive intermediates; the design of catalyst architectures that can provide effective enantiodifferentiating environments for these intermediates while minimizing the participation of uncontrolled racemic background processes has proven to be a key challenge for progress in this field. This review provides a summary of the chiral catalyst structures that have been studied for solution-phase asymmetric photochemistry, including chiral organic sensitizers, inorganic chromophores, and soluble macromolecules. While some of these photocatalysts are derived from privileged catalyst structures that are effective for both ground-state and photochemical transformations, others are structural designs unique to photocatalysis and offer an insight into the logic required for highly effective stereocontrolled photocatalysis.
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