Department of Chemistry, University of Cambridge, Cambridge, United Kingdom.
Nat Chem. 2020 Nov;12(11):990-1004. doi: 10.1038/s41557-020-00561-6. Epub 2020 Oct 22.
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.
过去十年中，新的化学方法的发展取得了前所未有的增长，这些方法的作用机制涉及自由基中间体。这种新的关注突显了自由基化学领域长期存在的一个挑战，即控制绝对立体化学。本综述将采用一种具有巨大潜力的策略来考察这些发展，该策略利用手性催化剂与底物之间的吸引力非共价相互作用来施加对映体控制。从简单的意义上讲，这种方法模拟了酶催化中的激活和控制模式，并且认识到在小分子催化剂的背景下可以实现这一点，这对近年来不对称催化领域产生了重大影响。这种策略现在开始迅速成为控制自由基反应对映选择性的有力方法，我们希望对目前进展的这一重点调查将激发该领域的未来发展。
