Remote steric control for undirected meta-selective C-H activation of arenes
Remote steric control for undirected meta-selective C-H activation of arenes
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DOI：
10.1126/science.abm7599
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发表时间：
2022-02-11
期刊：
影响因子：
56.9
通讯作者：
Ilies, Laurean
中科院分区：
文献类型：
--
作者：
Ramadoss, Boobalan;Jin, Yushu;Ilies, Laurean
芳烃的区域选择性功能化在有机合成中仍是一个具有挑战性的问题。空间相互作用经常被用来封闭与给定取代基相邻的位置，但它们不能区分剩余的远程位置。我们报道了一种基于远程空间控制的策略，即除了邻位外，屋顶状配体还保护远处的对位，从而在没有邻位或对位取代的情况下选择性地激活偏碳氢键。我们为各种单取代芳烃，包括复杂的药物分子，在Ir催化的偏选择性硼化反应中证明了这一概念。这一策略有可能将C-H键功能化工具箱扩展到以前不可微的反应位置。
Regioselective functionalization of arenes remains a challenging problem in organic synthesis. Steric interactions are often used to block sites adjacent to a given substituent, but they do not distinguish the remaining remote sites. We report a strategy based on remote steric control, whereby a roof-like ligand protects the distant para site in addition to the ortho sites, and thereby enables selective activation of meta carbon-hydrogen (C-H) bonds in the absence of ortho or para substituents. We demonstrate this concept for iridium-catalyzed meta-selective borylation of various monosubstituted arenes, including complex drug molecules. This strategy has the potential to expand the toolbox of C-H bond functionalization to previously nondifferentiable reaction sites.