武汉大学雷爱文团队报道了自由基引发的C-C双键和官能团的易位。相关研究成果发表在2024年9月9日出版的国际知名学术期刊《自然—化学》。

分子的多位点官能化为获得复杂的化合物提供了一种有效的方法。然而，反应位点和惰性远端C（sp3）-H的同时官能化带来了巨大的挑战，因为化学反应通常发生在最活跃的位点。此外，实现对远程C（sp3）-H激活的位点选择性的精确控制是一个额外的障碍。

该文中，研究人员报告了一种用于烯烃双官能化的替代模块化方法，包括自由基引发的官能团易位和通过光/钴双催化的远程C（sp3）-H去饱和。

通过系统地结合自由基加成、官能团迁移和钴促进的氢原子转移，成功地实现了碳-碳双键和另一个官能团的易位，具有精确的位点选择性和显著的E/Z选择性。

这种氧化还原中性方法与各种氟烷基和磺酰基前体具有良好的相容性，使苯甲酰氧基、乙酰氧基、甲酰基、氰基和杂芳基能够迁移。该协议为多个位点的同时转换提供了解决方案。

附：英文原文

Title: Radical-triggered translocation of C–C double bond and functional group

Author: Wang, Shengchun, Luo, Xu, Wang, Yuan, Liu, Zhao, Yu, Yi, Wang, Xuejie, Ren, Demin, Wang, Pengjie, Chen, Yi-Hung, Qi, Xiaotian, Yi, Hong, Lei, Aiwen

Issue&Volume: 2024-09-09

Abstract: Multi-site functionalization of molecules provides a potent approach to accessing intricate compounds. However, simultaneous functionalization of the reactive site and the inert remote C(sp3)–H poses a formidable challenge, as chemical reactions conventionally occur at the most active site. In addition, achieving precise control over site selectivity for remote C(sp3)–H activation presents an additional hurdle. Here we report an alternative modular method for alkene difunctionalization, encompassing radical-triggered translocation of functional groups and remote C(sp3)–H desaturation via photo/cobalt dual catalysis. By systematically combining radical addition, functional group migration and cobalt-promoted hydrogen atom transfer, we successfully effectuate the translocation of the carbon–carbon double bond and another functional group with precise site selectivity and remarkable E/Z selectivity. This redox-neutral approach shows good compatibility with diverse fluoroalkyl and sulfonyl radical precursors, enabling the migration of benzoyloxy, acetoxy, formyl, cyano and heteroaryl groups. This protocol offers a resolution for the simultaneous transformation of manifold sites.

DOI: 10.1038/s41557-024-01633-7

Source: https://www.nature.com/articles/s41557-024-01633-7