中国科学院上海有机化学研究所Zheng Huang团队通过钴/铁双催化实现了顺序氢硅烷化和异构化，从末端炔烃合成了三取代的(E)-烯基硅烷类化合物。该研究于2024年4月18日发表于国际一流学术期刊《中国化学》杂志上。

在该研究中，通过合理修饰螯合配体的电子和空间性质，研究者建立了一种Co/Fe双催化剂体系，用于一锅顺序马式炔的硅氢化和立体选择性烯烃异构化。该方案提供了一个原子经济和高效的方法，在温和条件下，从易获得的末端炔中以高区域选择性和立体选择性，合成三取代(E)-烯基硅烷类化合物。

团队还通过克级合成和生物活性分子的衍生化，证明了该反应的实用性。自由基时钟和捕获实验表明，自由基途径可能在烯烃异构化过程中起作用。

附：英文原文

Title: Co/Fe Dual Catalysis for Sequential Hydrosilylation–Isomerization: Access to Trisubstituted (E)-Alkenyl Silanes from Terminal Alkynes

Author: Zhihao Guo, Guixia Liu, Zheng Huang

Issue&Volume: 2024-04-18

Abstract: By rational modification of electronic and steric properties of pincer ligands, a Co/Fe dual catalyst system is developed for one-pot sequential Markovnikov alkyne hydrosilylation and stereoselective alkene isomerization. The protocol provides an atom-economical and efficient approach to trisubstituted (E)-alkenyl silanes from widely accessible terminal alkynes with high regio- and stereoselectivities under mild conditions. The utility of this reaction was demonstrated by gram-scale synthesis and derivatization of bioactive molecules. The radical clock and trapping experiments indicated that radical pathway might be operative in the alkene isomerization step.

DOI: 10.1002/cjoc.202400291

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202400291