Manipulating Reaction Energy Coordinate Landscape of Mechanochemical Diaza-Cope Rearrangement.
Manipulating Reaction Energy Coordinate Landscape of Mechanochemical Diaza-Cope Rearrangement.
复制标题
DOI：
10.3390/molecules27082570
复制
发表时间：
2022-04-15
期刊：
影响因子：
--
通讯作者：
中科院分区：
文献类型：
--
作者：
手性邻二胺是一类独特的光学活性构件，在材料设计、医药和催化等领域发挥着至关重要的作用。传统上，它们的合成都是基于溶剂的方法，这使得有机溶剂成为它们生产中不可或缺的一部分。作为我们旨在开发减少碳足迹的化学过程的计划的一部分，我们最近报道了一条高度实用和环保的合成手性邻二胺的路线，该路线是通过无溶剂的机械化学重氮化重排来实现的。我们在这里表明，与没有添加剂的反应相比，通过与常见的实验室固体添加剂(如硅胶)共磨的新方案可以显著提高反应效率。一种可能的解释是添加剂的刘易斯酸性，它加速了关键的希夫碱形成步骤。跟踪包括反应物、中间体和产物在内的所有反应物种的反应监测实验表明，反应轮廓与没有添加剂的球磨反应明显不同。综上所述，本工作证明了加性效应是控制机械力化学重氮化重排反应中反应途径的有力工具，这有望在以机械力为能量输入的有机合成中引起广泛的兴趣。
Chiral vicinal diamines, a unique class of optically-active building blocks, play a crucial role in material design, pharmaceutical, and catalysis. Traditionally, their syntheses are all solvent-based approaches, which make organic solvent an indispensable part of their production. As part of our program aiming to develop chemical processes with reduced carbon footprints, we recently reported a highly practical and environmentally-friendly synthetic route to chiral vicinal diamines by solvent-free mechanochemical diaza-Cope rearrangement. We herein showed that a new protocol by co-milling with common laboratory solid additives, such as silica gel, can significantly enhance the efficiency of the reaction, compared to reactions in the absence of additives. One possible explanation is the Lewis acidic nature of additives that accelerates a key Schiff base formation step. Reaction monitoring experiments tracing all the reaction species, including reactants, intermediates, and product, suggested that the reaction profile is distinctly different from ball-milling reactions without additives. Collectively, this work demonstrated that additive effect is a powerful tool to manipulate a reaction pathway in mechanochemical diazo-Cope rearrangement pathway, and this is expected to find broad interest in organic synthesis using mechanical force as an energy input.
登录
查看更多内容
影响因子：
8.4
作者：
Belenguer, Ana M.;Friscic, Tomislav;Sanders, Jeremy K. M.
通讯作者：
Sanders, Jeremy K. M.
影响因子：
8.4
作者：
Gao Y;Feng C;Seo T;Kubota K;Ito H
通讯作者：
Ito H
影响因子：
64.8
作者：
Giri, Nicola;Del Popolo, Mario G.;James, Stuart L.
通讯作者：
James, Stuart L.
影响因子：
2.9
作者：
HETTINGE.TP;CRAIG, LC
通讯作者：
CRAIG, LC
影响因子：
7.3
作者：
GUST, R;BURGEMEISTER, T;SCHONENBERGER, H
通讯作者：
SCHONENBERGER, H