Visible Light-Driven Radical trans-Hydrosilylation of Electron-Neutral and -Rich Alkenes with Tertiary and Secondary Hydrosilanes
Visible Light-Driven Radical trans-Hydrosilylation of Electron-Neutral and -Rich Alkenes with Tertiary and Secondary Hydrosilanes
复制标题
电子中性和富烯烃与叔氢和仲氢硅烷的可见光驱动自由基反氢化硅烷化
DOI：
10.1021/acs.joc.8b02409
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发表时间：
2018
影响因子：
3.6
通讯作者：
Yao Zhu-Jun
中科院分区：
文献类型：
--
作者：
Zhu Jing;Cui Wei-Chen;Wang Shaozhong;Yao Zhu-Jun
在新开发的由伊红Y、硫醇和碱添加剂组成的催化反应体系的基础上，研究了富电子中性烯烃的可见光自由基硅氢化反应。各种具有不同取代模式的线性和环状烯烃被发现以化学、区域和立体选择的方式与叔氢硅烷和仲氢硅烷进行无金属硅氢化反应。对二烯类化合物的反应性和类固醇药物的硅氢化后期反应性进行了比较。氘标记实验表明，C-Si和C-H键的逐步形成是首选的，其中硫醇可能作为氢原子转移剂。
A visible light-driven radical hydrosilylation of electron-neutral and -rich alkenes has been investigated on the basis of a newly developed catalytic reaction system composed of eosin Y, thiol, and base additives. A variety of linear and cyclic alkenes with different substitution patterns were found to undergo such metal-free hydrosilylation with tertiary and secondary hydrosilanes in a chemo-, regio-, and stereoselective manner. Comparison of the reactivity of diene compounds and late-stage hydrosilylation of steroid drugs were also explored. Deuterium labeling experiments reveal that a stepwise formation of C–Si and C–H bonds with atransstereochemistry is preferred, in which the thiol may behave as a hydrogen atom transfer agent.