The sequential combination of the facile substitution of organohalides with the nitrile function and the hydroboration of the resultant nitriles enables a straight-forward access to synthetically versatile primary amines via a formal C₁ homologation. Several catalysts have been reported for the latter transformation, mostly with transition metal catalysts (Ti, Fe, Co, Ni, Zn, Ru, Mo). Very few main group metal catalysts have been demonstrated to show equal activity. This work reports an operationally facile hydroboration of nitriles at room temperature that operates under catalysis of the solid, stable, and inexpensive salt lithium hexamethyldisilazide, LiN(SiMe₃)₂. The reaction displayed good tolerance of functional groups including F, Cl, Br, I, pyridyl, and thiophene substituents. Carbonyl derivatives readily reacted under the same conditions. Mechanistic studies were indicative of the catalytic role of lithium amidinate intermediates, the co-catalytic role of nitrile additives, and a reaction order of zero in borane.

中文翻译：

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锂酰胺催化的腈加氢硼化

易于将有机卤化物取代并具有腈官能团和所得腈进行硼氢化反应的顺序组合，可以通过正式的C ₁同源性直接获得合成通用的伯胺。已经报道了用于后一种转化的几种催化剂，主要是过渡金属催化剂（Ti，Fe，Co，Ni，Zn，Ru，Mo）。已经证明很少有主族金属催化剂显示出相同的活性。这项工作报告了在室温下腈的易操作的硼氢化反应，该反应在固体，稳定且便宜的六甲基二硅化锂LiN（SiMe ₃）_2的催化下进行。该反应显示出对包括F，Cl，Br，I，吡啶基和噻吩取代基的官能团的良好耐受性。羰基衍生物容易在相同条件下反应。机理研究表明mid酰胺锂中间体的催化作用，腈添加剂的共催化作用以及硼烷中的零反应阶数。