有吸引力的非共價相互作用實現自由基反應的對映選擇性催化

有吸引力的非共價相互作用實現自由基反應的對映選擇性催化

作者：

小柯機器人

發布時間：2020/10/28 12:50:41

劍橋大學Robert J. Phipps研究團隊近日發表一項綜述。他們概括了利用非共價相互吸引作用實現涉及自由基中間體的不對稱催化反應。 相關論文於2020年10月22日發表在《自然—化學》雜誌上。

這篇綜述文章探討了解決這一挑戰（對反應產物的絕對構型控制）的一種有巨大潛力的策略，即利用手性催化劑與底物之間有吸引力的非共價相互作用來實現在自由基反應中對映體產物構型的控制。簡單來說，這一策略模擬了酶催化和對底物的活化。並且在小分子催化領域實現這一策略已經在近年取得了巨大影響。現在，這一策略開始被用於控制自由基反應中產物的絕對構型。研究小組希望這一綜述可以激發本領域的進一步發展。

過去的十年中，利用自由基中間體實現新的化學反應取得了巨大的進展。這一進展突出了自由基化學領域的一個長期存在的挑戰，即對反應產物的絕對構型的控制。

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