Department of Applied Chemistry, Graduate School of Engineering, Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, 2-1 Yamadaoka, Suita, Osaka 565-0871, Japan.
J Am Chem Soc. 2021 Dec 15;143(49):20616-20621. doi: 10.1021/jacs.1c10517. Epub 2021 Nov 12.
Selective transformation of C-F bonds remains a significant goal in organic chemistry, but C-F insertion of a one-carbon-atom unit has never been established. Herein we report the BF-catalyzed formal insertion of diazo esters as one-carbon-atom sources into C-F bonds to accomplish one-carbon elongation of benzylic fluorides. A DFT calculation study revealed that the BF catalyst could contribute to both C-F bond cleavage and re-formation. This elongation provided α-fluoro-α,β-diaryl esters with a high level of diastereoselectivity. Various benzylic fluorides and diazo esters were applicable. The synthetic utility of this method was demonstrated by the synthesis of a fluoro analogue of a compound that is used as a transient receptor and potential canonical channel inhibitor.
选择性转化 C-F 键仍然是有机化学中的一个重要目标，但从未建立过一碳单元的 C-F 插入。在此，我们报告了 BF 催化的重氮酯作为一碳源的形式插入到 C-F 键中，以完成苄基氟化物的一碳延伸。DFT 计算研究表明，BF 催化剂可以促进 C-F 键的断裂和重新形成。这种延伸提供了具有高水平非对映选择性的α-氟-α,β-二芳基酯。各种苄基氟化物和重氮酯都适用。该方法的合成实用性通过合成一种用作瞬时受体和潜在经典通道抑制剂的氟类似物得到了证明。
