Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium
Unprecedented Nucleophilic Additions of Highly Polar Organometallic Compounds to Imines and Nitriles Using Water as a Non-Innocent Reaction Medium
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DOI：
10.1002/anie.201705412
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发表时间：
2017-08-14
影响因子：
16.6
通讯作者：
Perna, Filippo Maria
中科院分区：
文献类型：
--
作者：
Dilauro, Giuseppe;Dell' Aera, Marzia;Perna, Filippo Maria
与在干燥挥发性有机溶剂和低温惰性气氛下进行的经典方法相比，在室温和空气中以水作为唯一的反应介质，在广泛的底物上快速，有效和化学选择性地将高极性有机金属化合物添加到非活化亚胺和腈中。仲胺和叔胺的产率可达99%以上。观察到有机锂化合物在亚胺上的亲核添加的显著的溶剂D/H同位素效应表明，在水中的催化是由质子在有机-水界面上的转移引起的。水分子间强大的分子间氢键可能在不利于质子解的过程中起关键作用，而质子解在其他质子介质（如甲醇）中广泛存在。这项工作为重塑许多基本的s-block金属在水中介导的有机转化奠定了基础。
In contrast to classic methods carried out under 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 and over 99%. The significant solvent D/H isotope effect observed for the on-water nucleophilic additions of organolithium compounds to imines suggests that the on-water catalysis arises from proton transfer across the organic-water interface. The strong inter-molecular hydrogen bonds between water molecules may play a key role in disfavoring protonolysis, which occurs extensively in other protic media such as methanol. This work lays the foundation for reshaping many fundamental s-block metal-mediated organic transformations in water.