2020年12月14日出版的《自然·化学》杂志报道了南京大学谢劲团队的最新成果，他们开发出一种锰催化的烯烃发散烷基化反应。

在这项研究中，研究团队报告了一种利用锰催化对烯烃进行脱氢硅烷化和加氢硅烷化的简单普适的方法，该方法使用Mn₂(CO)₁₀作为催化剂前体并采取配体调节活性的金属自由基策略。这使得反应可在1:1的烯烃和硅烷之间发生并具备灵活性和可控选择性，而该方法的抗干扰性和实用性通过复杂烯烃和短烯烃上的反应得到了展示。

研究人员还通过密度泛函理论计算研究了该反应的选择性，结果表明使用ⁱPrPNP作为配体倾向于脱氢硅烷化，而使用JackiePhos配体倾向于加氢硅烷化。该反应是氧化还原中性和原子经济性的，表现出广阔的底物适应性和官能团兼容性，适用于许多克级合成应用中。

据了解，过渡金属催化的、氧化还原中性的烯烃脱氢硅烷化反应是有机合成中的一个长久以来的挑战，目前现有的方法存在选择性差和底物范围窄等问题。

附：英文原文

Title: Manganese-catalysed divergent silylation of alkenes

Author: Jie Dong, Xiang-Ai Yuan, Zhongfei Yan, Liying Mu, Junyang Ma, Chengjian Zhu, Jin Xie

Issue&Volume: 2020-12-14

Abstract: Transition-metal-catalysed, redox-neutral dehydrosilylation of alkenes is a long-standing challenge in organic synthesis, with current methods suffering from low selectivity and narrow scope. In this study, we report a general and simple method for the manganese-catalysed dehydrosilylation and hydrosilylation of alkenes, with Mn2(CO)10 as a catalyst precursor, by using a ligand-tuned metalloradical reactivity strategy. This enables versatility and controllable selectivity with a 1:1 ratio of alkenes and silanes, and the synthetic robustness and practicality of this method are demonstrated using complex alkenes and light olefins. The selectivity of the reaction has been studied using density functional theory calculations, showing the use of an iPrPNP ligand to favour dehydrosilylation, while a JackiePhos ligand favours hydrosilylation. The reaction is redox-neutral and atom-economical, exhibits a broad substrate scope and excellent functional group tolerance, and is suitable for various synthetic applications on a gram scale.

DOI: 10.1038/s41557-020-00589-8

Source: https://www.nature.com/articles/s41557-020-00589-8