Pradhan Subham, Sankar Raman Vijaya, Gunanathan Chidambaram
School of Chemical Sciences, National Institute of Science Education and Research (NISER), An OCC of Homi Bhabha National Institute, Bhubaneswar 752050, India.
J Org Chem. 2022 Sep 16;87(18):12386-12396. doi: 10.1021/acs.joc.2c01655. Epub 2022 Aug 31.
Organoborane-catalyzed hydroboration of nitriles provides ,-diborylamines, which act as efficient synthons for the synthesis of primary amines and secondary amides. Known nitrile hydroboration methods are dominated by metal catalysis. Simple and metal-free hydroboration of nitriles using diborane [H-B-9-BBN] as a catalyst and pinacolborane as a turnover reagent is reported. The reaction of monomeric H-B-9-BBN with nitriles leads to the hydrido-bridged diborylimine intermediate; a subsequent sequential double hydroboration-transborylation pathway involving B-N/B-H σ bond metathesis is proposed.
有机硼烷催化的腈硼氢化反应可生成α,β-二硼基胺，其可作为合成伯胺和仲酰胺的有效合成子。已知的腈硼氢化方法主要以金属催化为主。本文报道了以二硼烷[H-B-9-BBN]为催化剂、频哪醇硼烷为周转试剂，对腈进行简单的无金属硼氢化反应。单体H-B-9-BBN与腈的反应生成氢化桥连二硼基亚胺中间体；提出了一种随后涉及B-N/B-H σ键复分解的连续双硼氢化-转硼化途径。
