2025-12-09 北海道大学
メカノケミカル法を用いることで、空気下・室温で有機溶媒をほとんど使用せずに、安価な金属ナトリウムから有機ナトリウム試薬を調製し、有機合成に利用することに成功。
＜関連情報＞
- https://www.hokudai.ac.jp/news/2025/12/post-2137.html
- https://www.hokudai.ac.jp/news/pdf/251209_pr.pdf
- https://www.nature.com/articles/s44160-025-00949-7
有機ハロゲン化物の直接ナトリウム化による有機ナトリウム試薬のメカノケミカル合成Mechanochemical synthesis of organosodium compounds through direct sodiation of organic halides
Keisuke Kondo,Matthew Lowe,Nathan Davison,Paul G. Waddell,Roly J. Armstrong,Erli Lu,Koji Kubota & Hajime Ito
Nature Synthesis Published:08 December 2025
DOI:https://doi.org/10.1038/s44160-025-00949-7
Abstract
Organometallic reagents are essential in organic synthesis, with organolithium compounds being most widely used. However, as lithium becomes less abundant and increasingly expensive, organosodium compounds have emerged as promising alternatives, but their use in organic synthesis is limited by their poor solubility in organic solvents, the need for pre-activated sodium sources and the necessity for highly anhydrous conditions. Here we report a mechanochemical protocol for the direct generation of organosodium compounds from cheap and shelf-stable sodium lumps and readily available organic halides under bulk, solvent-free conditions. These reactions generate an array of organosodium compounds in minutes, without special precautions against moisture or temperature control. These nucleophiles can be used directly for one-pot nucleophilic addition reactions with electrophiles and nickel-catalysed cross-coupling reactions. Furthermore, this mechanochemical approach enables the sodiation of inert C–F bonds in organic fluorides. This method is anticipated to drive progress in sodium-based synthetic chemistry.
