SusChEM: Supramolecular chaperones for organic reactions in water

化学部的大分子、超分子和纳米化学项目正在资助斯克里普斯研究所的朱利叶斯·雷贝克教授研究水中有机反应的超分子“伴侣”。目前，工业上进行的大多数化学反应都是在有机溶剂中进行的，这些溶剂通常是从石油化工产品中获得的。本提案旨在研究如何在水中进行这些反应。这项研究涉及使用新的合成化合物作为小分子的容器。当分子在容器内时，它们会采用新的形状，以增加已知反应的可能性，并使容器外未知的反应在水中发生。提出的基础研究以科学训练和发现为目标；提出的应用研究旨在发明将化学反应从石化产品的限制转移到最环保、最便宜的溶剂——水上。这个提议打算应用合成的、水溶性的容器宿主“空腔体”来改变里面小分子的行为。空腔体结合它们的目标客体，暂时将它们与水介质隔离，将它们置于疏水环境中，并将它们折叠成活性形状。空腔在一定的pH值范围内起作用，并以埋住来宾的疏水部分并使其末端靠近的构象占据烃链。客体分子的不寻常形状将被利用来引导反应沿着不可能的路径，甚至是在散装溶液中未知的路径。u型排列可以促进许多大环反应和远端官能化反应。将测试强制转换和促进水中空腔催化的策略。这些应用与现有的模板效应和通常在有机介质中进行的原子转移反应的方法不同。

With this award, the Macromolecular, Supramolecular and Nanochemistry Program in the Chemistry Division is funding Professor Julius Rebek of the Scripps Research Institute to study supramolecular "chaperones" for organic reactions in water. Currently the majority of chemical reactions performed in industry take place in organic solvents, solvents that are generally obtained from petrochemicals. This proposal intends to research how those reactions could be performed in water. The research involves the use of new synthetic compounds that act as containers for smaller molecules. While molecules are inside the containers, they adopt new shapes that increase their probability for known reactions and make possible reactions that are unknown outside the containers in water. The basic research proposed is targeted at scientific training and discovery; the applied research proposed is aimed at inventions that move chemical reactions from the limitations of petrochemicals into the most ecofriendly and least expensive solvent, water.This proposal intends to apply synthetic, water-soluble container hosts "cavitands" to alter the behavior of small molecules held inside. Cavitands bind their target guests, temporarily isolate them from the aqueous medium, place them a hydrophobic environment and fold them into reactive shapes. The cavitands operate over a range of pH and take up hydrocarbon chains in conformations that bury the hydrophobic parts of the guests and bring their ends close together. The unusual shape of the guest molecules will be harnessed to guide reactions along pathways that are improbable, or even unknown in bulk solution. The U-shaped arrangements can promote a number of macrocyclic processes and remote functionalization reactions. Tactics to force turnover and promote catalysis with the cavitands in water will be tested. The applications are departures from existing methods involving template effects and atom transfer reactions that are typically performed in organic media.