Liu Han-Ying, Hill Michael S, Mahon Mary F
Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, UK.
Chem Commun (Camb). 2022 Jun 16;58(49):6938-6941. doi: 10.1039/d2cc02333d.
The reactivity of a seven-membered cyclic potassium diamidoalumanyl toward a variety of ketone small molecules has been assessed. Whilst acetophenone generates an aluminium pinacolate derivative, reductive C-C coupling is induced between the ketyl and -carbon centres of two equivalents of benzophenone. In contrast, whereas oxidative addition of an enolisable proton is observed with 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone undergoes an unprecedented hydroalumination process, where the reducing hydride may be traced to intramolecular oxidative addition of a (sp)C-H bond.
已评估了一种七元环状二氨基铝钾对多种酮小分子的反应活性。虽然苯乙酮生成了一种频哪醇铝衍生物，但在两当量二苯甲酮的酮基和α-碳中心之间诱导了还原型碳-碳偶联。相比之下，虽然观察到2,4-二甲基-3-戊酮发生了可烯醇化质子的氧化加成，但2,2,4,4-四甲基-3-戊酮经历了一个前所未有的氢化铝化过程，其中还原氢化物可追溯到一个(sp)C-H键的分子内氧化加成。
