School of Chemical Sciences, University of Illinois at Urbana-Champaign , 600 S. Mathews Avenue, Urbana, Illinois 61801, United States.
J Am Chem Soc. 2017 Sep 27;139(38):13554-13561. doi: 10.1021/jacs.7b07368. Epub 2017 Sep 14.
The selective hydrogenation of nitriles to primary amines using a bench-stable cobalt precatalyst under 4 atm of H is reported herein. The catalyst precursor was reduced in situ using NaHBEt, and the resulting Lewis acid formed, BEt, was found to be integral to the observed catalysis. Mechanistic insights gleaned from para-hydrogen induced polarization (PHIP) transfer NMR studies revealed that the pairwise hydrogenation of nitriles proceeded through a Co(I/III) redox process.
本文报道了在 4 个大气压的 H 下，使用稳定的钴前催化剂将腈选择性氢化生成伯胺。催化剂前体通过 NaHBEt 原位还原，形成的路易斯酸 BEt 被发现对观察到的催化作用至关重要。从氘氢诱导极化（PHIP）转移 NMR 研究中获得的机理见解表明，腈的成对氢化通过 Co(I/III)氧化还原过程进行。
