自由基反应的立体选择性调控一直是不对称催化领域的挑战性难题.近年来,光化学过程特别是可见光化学过程在有机合成中越来越受到研究人员的重视,光诱导自由基化学也再次进入人们的视野.相对传统的自由基化学,光诱导自由基化学反应条件温和,易于调控,为实现高效催化不对称自由基反应带来了新的契机,展示了蓬勃的发展潜力.本文根据光诱导产生自由基种类的不同,简要介绍最近该方向的研究进展.
Enantioselective control of free radical reactions has eluded organic chemists for decades. Echoed with the renaissance of photo-induced processes, or so called photocatalysis or photoredox catalysis in organic synthesis, photo-induced organic radical chemistry has regained its prominence in developing catalytic asymmetric radical reaction. The generally mild conditions inherited with photochemistry, particularly visible light photo-processes, have allowed for controllable generation of free radicals as well as the subsequent bond formations. The past five years have witnessed dramatic advances in exploring photo-induced catalytic asymmetric free radical reactions, and enormous potentials along this line are envisaged. This perspective gives a brief summary on the important advances in this field. Accordingly, the major advances are classified based on different radical species including α-amino/oxyl radicals, radicals generated from enones and its analogues, benzyl radicals, α-carbonyl radicals, polyhalogenated alkyl radicals and nitrogen radicals. Brief discussion of mechanism is presented whenever relevant.