激进的
化学
笼子
笼效应
反应机理
光化学
溶剂
结果(博弈论)
反应中间体
计算化学
有机化学
催化作用
数理经济学
数学
组合数学
光解
作者
Zihang Qiu,Constanze N. Neumann
标识
DOI:10.1021/acsorginorgau.3c00044
摘要
Radical reactions have recently experienced a resurgence in organic chemistry after many decades of being considered to be too unselective to offer a viable solution for complex synthetic problems. Radical intermediates often have a number of different reaction pathways available to them that are all associated with insubstantial reaction barriers so that reaction outcomes can be controlled by proximity and dynamics. Cage effects consist of the effect of the surrounding medium, such as the solvent or the enzyme pocket, on the movement of radical intermediates and the medium’s resulting influence over reaction outcomes and selectivity. Cage effects substantially affect the outcome of all transformations in condensed phases, which feature the intermediacy of radical pairs, and a suitable choice of the cage should thus constitute a key optimization parameter for radical reactions. This Perspective provides an overview of key aspects of the cage effect that can be of importance in synthetic chemistry and highlights its role in a number of recently reported transformations that forge C–X bonds via the intermediacy of radicals.
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