Ding Yuxuan, Luo Shihui, Ma Lifu, An Jie
College of Science , China Agricultural University , No. 2, Yuanmingyuan West Road , Beijing 100193 , China.
School of Precision Instrument and Opto-Electronics Engineering , Tianjin University , Tianjin 300072 , China.
J Org Chem. 2019 Dec 20;84(24):15827-15833. doi: 10.1021/acs.joc.9b02028. Epub 2019 Nov 15.
A general protocol for the reductive cleavage of unactivated carbon-cyano bonds in aliphatic nitriles has been achieved under single-electron-transfer conditions using Na/15-crown-5/HO. Electron is supplied by the electride derived from bench-stable sodium dispersions and recoverable 15-crown-5. HO provides the proton source and suppresses the reduction of aromatic moieties. Compared with the Na/NH electride system generated under traditional Birch conditions, this ammonia-free electride system is more practical and features better reactivity and chemoselectivity for the decyanations of a broad range of aliphatic nitriles.
在单电子转移条件下，使用钠/15-冠-5/水实现了脂肪腈中未活化碳-氰基键的还原裂解通用方案。电子由源自稳定钠分散体和可回收的15-冠-5的电子化物提供。水提供质子源并抑制芳环部分的还原。与传统Birch条件下生成的钠/液氨电子化物体系相比，这种无氨电子化物体系更实用，对多种脂肪腈的脱氰反应具有更好的反应性和化学选择性。
