重庆大学药学院Zhang Feng团队进行了铁催化非活性脂肪族偕二氟烯烃选择性、可控去氟硅化反应的实验和计算研究。 相关论文发表在2021年2月8日出版的《德国应用化学》杂志上。

课题组开发了第一个铁催化的未活化偕二氟烯的去氟硅化反应，以优异的效率生成偕二硅化烯烃和E-硅化烯烃。该方案具有良好的官能团相容性、出色的区域选择性和立体选择性，可实现生物相关化合物的后期甲硅烷基化，从而为药物化学应用提供了良好的机会。

初步的机理研究和DFT计算表明，二硅烯化催化体系可能涉及亲核加成和消除第二个C-F键，这表明铁催化具有不同寻常的反应活性特点。

附：英文原文

Title: Experimental and Computational Studies on the Iron‐Catalyzed Selective and Controllable Defluorosilylation of Unactivated Aliphatic gem‐Difluoroalkenes

Author: Zhang Feng, Huan Zhang, Enhui Wang, Shasha Geng, Zhengli Liu, Yun He, Qian Peng

Issue&Volume: 2021-02-08

Abstract: The first iron‐catalyzed defluorosilylation of unactivated gem‐difluoroalkenes is developed, delivering gem‐disilylated alkenes and E‐silylated alkenes with excellent efficiency. This protocol features good functional group compatibility, and excellent regio‐ and stereo‐selectivity, enabling the late‐stage silylation of bio‐relevant compounds, thus providing good opportunities for applications in medicinal chemistry. Preliminary mechanistic studies and DFT calculations reveal that a nucleophilic addition and elimination of the second C‐F bond might be involved in the disilylation catalytic system, demonstrating unusual reactivity characteristics of iron catalysis.

DOI: 10.1002/anie.202100049

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202100049