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.

在过去的十年中，通过涉及自由基中间体的机制进行的新化学方法的开发取得了前所未有的增长。这种新的关注凸显了自由基化学领域长期存在的挑战——控制绝对立体化学的挑战。本综述将使用具有巨大潜力的策略来研究开发，其中利用手性催化剂和底物之间有吸引力的非共价相互作用来施加对映控制。从简单的意义上讲，这种方法模仿了酶催化中的活化和控制模式，并且认识到这可以在小分子催化剂的背景下实现，近年来对不对称催化领域产生了相当大的影响。