可见光促进有机硅化合物参与的化学转化

Progress in Visible-Light Promoted Transformations of Organosilicon Compounds

有机硅化合物具有重要用途,被广泛应用于材料科学与药物化学等领域.因此,有机硅试剂参与的化学转化一直倍受关注.近年来,可见光催化迅速发展,为有机合成化学提供了新的机遇.在光氧化还原体系下,有机硅试剂可以经由氢原子转移(Hydrogen atom transfer,HAT)或单电子转移(Single electron transfer,SET)过程转化为硅自由基或碳自由基进行反应,具有条件温和、选择性好和原子经济性高等优势.根据反应类型不同,主要综述了有机硅试剂作为硅自由基前体参与的烯(炔)烃硅氢化反应、烯(炔)烃双官能化反应、氮杂芳烃的硅基化反应,以及有机硅化合物作为碳自由基前体参与的亲核加成反应、Minisci反应、均裂取代反应和过渡金属介导的交叉偶联反应.

Organosilicon compounds play important roles in the fields of material science and pharmaceutical chemistry.The transformations involving organosilicon reagents have therefore attract extensive interest from synthetic community.The burgeoning visible light photocatalysis has provided a new opportunity for organic synthesis.Under the photoredox system,organosilicon compounds could be transformed into silicon or carbon radicals to participate in a variety of reactions.Generally,these reactions bear the merits,such as mild conditions,good selectivity,as well as high atom economy.According to the types of reactions,the recent progress in visible-light mediated hydrosilylation and difunctionalization of alkenes and alkynes,C—H bond silylation of N-aromatic heterocycles using organosilicon compounds as silicon radical precursors,and nucleophilic addition,Minisci reaction,homolytic substitution,as well as transition metal mediated cross-coupling reactions using organosilicon compounds as carbon radical precursors is reviewed primarily herein.