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有吸引力的非共价相互作用实现自由基反应的对映选择性催化
作者:小柯机器人 发布时间:2020/10/28 12:50:41

剑桥大学Robert J. Phipps研究团队近日发表一项综述。他们概括了利用非共价相互吸引作用实现涉及自由基中间体的不对称催化反应。 相关论文于2020年10月22日发表在《自然—化学》杂志上。

这篇综述文章探讨了解决这一挑战(对反应产物的绝对构型控制)的一种有巨大潜力的策略,即利用手性催化剂与底物之间有吸引力的非共价相互作用来实现在自由基反应中对映体产物构型的控制。简单来说,这一策略模拟了酶催化和对底物的活化。并且在小分子催化领域实现这一策略已经在近年取得了巨大影响。现在,这一策略开始被用于控制自由基反应中产物的绝对构型。研究小组希望这一综述可以激发本领域的进一步发展。

过去的十年中,利用自由基中间体实现新的化学反应取得了巨大的进展。这一进展突出了自由基化学领域的一个长期存在的挑战,即对反应产物的绝对构型的控制。

附:英文原文

Title: Exploiting attractive non-covalent interactions for the enantioselective catalysis of reactions involving radical intermediates

Author: Rupert S. J. Proctor, Avene C. Colgan, Robert J. Phipps

Issue&Volume: 2020-10-22

Abstract: The past decade has seen unprecedented growth in the development of new chemical methods that proceed by mechanisms involving radical intermediates. This new attention has served to highlight a long-standing challenge in the field of radical chemistry — that of controlling absolute stereochemistry. This Review will examine developments using a strategy that offers enormous potential, in which attractive non-covalent interactions between a chiral catalyst and the substrate are leveraged to exert enantiocontrol. In a simplistic sense, such an approach mimics the modes of activation and control in enzyme catalysis and the realization that this can be achieved in the context of small-molecule catalysts has had sizable impact on the field of asymmetric catalysis in recent years. This strategy is now starting to quickly gather pace as a powerful approach for control of enantioselectivity in radical reactions and we hope that this focused survey of progress so far will inspire future developments in the area.

DOI: 10.1038/s41557-020-00561-6

Source: https://www.nature.com/articles/s41557-020-00561-6

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex