过渡金属催化的硅烷基C(sp^(3))–H键活化  

Transition-metal-catalyzed cleavage of silyl C(sp^(3))–H bonds

作　　者：杨勇 刘俊 欧阳昆冰 席振峰[2] Yong Yang;Jun Liu;Kunbing Ouyang;Zhenfeng Xi(Hunan Province Key Laboratory of Green Organic Synthesis and Application,Key Laboratory of Environmentally Friendly Chemistry and Application of Ministry of Education,College of Chemistry,Xiangtan University,Xiangtan 411105,China;Beijing National Laboratory for Molecular Sciences,College of Chemistry,Peking University,Beijing 100871,China)

机构地区：[1]湘潭大学化学学院,绿色有机合成与应用湖南省重点实验室,环境友好化学与应用教育部重点实验室,湘潭411105 [2]北京大学化学与分子工程学院,北京分子科学国家实验室,北京100871

出　　处：《中国科学：化学》2021年第2期97-109,共13页SCIENTIA SINICA Chimica

基　　金：国家自然科学基金(编号:21602188)资助项目。

摘　　要：有机硅化合物在有机合成、材料化学和药物化学中都有广泛应用.因此,其自身的合成方法学在近年来广受关注.从原子经济性的角度出发,选择性的C(sp^(3))–H键切断是一种高效经济的合成策略.硅烷基单元在有机化合物中广泛存在,通过对硅烷基中的C(sp^(3))–H键直接官能团化来合成新的有机硅化合物是一种十分有前景的合成方法.近年来,过渡金属催化的C(sp^(3))–H键活化成为有机合成研究的热点领域.与肟基、唑啉、吡啶基、酰胺基、羧酸酯基等官能团或是与氧、氮或硫等杂原子相连的C(sp^(3))–H键的活化研究已有许多报道,但是与硅相邻的C(sp^(3))–H键活化研究报道很少.本文综述了近年来过渡金属催化的硅烷基C(sp^(3))–H键切断的研究进展.Organosilicons are widely used in organic synthetic chemistry, materials science, and medicinal chemistry.Therefore, synthetic methodologies for organosilicons have been attractive. Selective cleavage of C(sp^(3))–H bonds is an effective synthetic strategy with high atom economy. Alkylsilyl groups are among the most frequently encountered functional groups which have been widely applied in organic synthesis. Direct functionalization of C(sp^(3))–H bonds of the alkylsilyl groups is an ideal and powerful strategy for the synthesis of organosilicons. Transition-metal-catalyzed cleavage of C(sp^(3))–H bonds has become a hot spot in the field of organic synthesis. Although the cleavage of the C(sp^(3))–H bonds adjacent to oxime, oxazoline, pyridine, amide, carboxyl, hetero-atoms such as N, O, S have been well studied,only a few cases of the direct functionalization of the C(sp^(3))–H bonds adjacent to Si have been reported. This review summarizes recent reports on transition-metal-catalyzed cleavage of silyl C(sp^(3))–H bonds.

关 键 词：三甲基硅基 切断C(sp^(3))–H键 过渡金属催化 C(sp^(3))–H键活化 合成有机硅化合物 

分 类 号：O621.251[理学—有机化学]