Catalytic formation of a regio- and enantioselective C–F bond chiral center from readily available alkenes is a crucial goal, yet it continues to pose significant challenges in organic synthesis. Here, we report the regioselective formation of C–F bonds facilitated by NiH catalysis and a coordination directing strategy that enables precise hydrofluorination of both terminal and internal alkenes. Notably, we have optimized this methodology to achieve high enantioselectivity in creating aliphatic C–F stereogenic centers especially with β,γ-alkenyl substrates, using a tailored chiral Bn-BOx ligand. Another pivotal finding in our research is the identification of the (+)-nonlinear effect under optimized conditions, allowing for high enantioselectivity even with moderately enantiomerically enriched chiral ligands. Given the significant role of fluorine in pharmaceuticals and synthetic materials, this research offers essential insights into the regioselective and enantioselective formation of C–F bond chiral centers, paving the way for the efficient production of valuable fluorinated compounds.

中文翻译：

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未活化烯烃中镍催化的氢氟化反应：区域选择性和对映选择性 C-F 键形成

从容易获得的烯烃中催化形成区域和对映选择性 C-F 键手性中心是一个至关重要的目标，但它仍然对有机合成提出了重大挑战。在这里，我们报告了 NiH 催化促进的 C-F 键的区域选择性形成以及能够实现末端和内部烯烃的精确氢氟化的配位指导策略。值得注意的是，我们使用定制的手性 Bn-BOx 配体优化了这种方法，以在创建脂肪族 C-F 立构中心（尤其是 β,γ-烯基底物）时实现高对映选择性。我们研究中的另一个关键发现是在优化条件下鉴定了 (+)-非线性效应，即使对于适度对映体富集的手性配体也能实现高对映选择性。鉴于氟在药物和合成材料中的重要作用，这项研究为 C-F 键手性中心的区域选择性和对映选择性形成提供了重要的见解，为高效生产有价值的氟化化合物铺平了道路。