Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium
作者:Giuseppe Dilauro、Marzia Dell'Aera、Paola Vitale、Vito Capriati、Filippo Maria Perna
DOI:10.1002/anie.201705412
日期:2017.8.14
inert atmospheres with dry volatile organic solvents and often low temperatures, the addition of highly polar organometallic compounds to non‐activated imines and nitriles proceeds quickly, efficiently, and chemoselectively with a broad range of substrates at room temperature and under air with water as the only reaction medium. Secondary amines and tertiary carbinamines are furnished in yields of up to
与在惰性气氛下使用干燥的挥发性有机溶剂并通常在低温下进行的经典方法相比,在非活化的亚胺和腈中向非活化亚胺和腈中添加高极性有机金属化合物可快速,高效且在室温下对多种底物进行化学选择性并在空气中以水为唯一反应介质。仲胺和叔卡宾胺的收率高达99%以上。在有机亚胺化合物向亚胺的水上亲核加成中观察到的显着的溶剂D / H同位素效应表明,水上催化源自质子跨有机-水界面的转移。水分子之间的强分子间氢键可能在不利于质子分解的过程中起关键作用,在其他质子传递介质(例如甲醇)中广泛存在。这项工作为重塑水中许多基本的s-block金属介导的有机转化奠定了基础。