Dream Fellowship. Innovations in Catalysis

这个建议是为了授予一个奖学金，使我能够把我的时间完全投入到研究活动中。我有两个主要领域准备发展，但这个奖学金的另一个特点是，额外的想法将出现在赠款的过程中。这将通过参与创造性解决问题的训练来培养创造力来实现。首先，我将研究从甘油三酯制备生物燃料。实现该反应的常规方法是与甲醇的酯交换，其释放甘油作为必须除去的废物。从概念上讲，甘油酯主链中C-C键的氢解将以完全原子有效的方式产生生物柴油（FAME;脂肪酸甲酯），而不形成甘油。发展一个可行的策略来选择性氢解C-C键将是一个强大的合成方法，但它将是一个非常坚韧的问题来解决。将其应用于生物柴油合成将产生令人难以置信的影响-2008年欧洲的生物柴油产量接近800万吨！其次，我想发展一种新的策略来合成双齿配体，我称之为金属配体。核心思想是制备通式X-X-PR 2的非常简单的单齿膦（或其他供体），其中X基团是氧或氮，并且间隔基团将是容易偶联的单元，其可以是对映体纯的。一种金属，如镁，或者镧系元素，将与X基团结合，产生双齿膦，而不存在通常的合成挑战。第二种金属，如钌或镍，将与膦结合，成为系综的催化核心。我们可以对膦的咬角进行细微的改变;想象一下镧系元素收缩的过程;想象一下改变第一种金属的几何形状来改变配体的构象。第一金属可以是刘易斯酸，并且与适当的间隔基一起，在第二金属位点以高区域选择性活化分子。催化的可能性似乎是无限的，但需要时间将这些想法转化为实际的解决方案。

This proposal is for the award of a fellowship which will allow me to devote my time solely to research activities. I have two main areas ready for development, but an additional feature of this fellowship is that additional ideas will emerge during the course of the grant. This will be achieved by fostering creativity by involvement with training in creative problem solving.Firstly, I will investigate the preparation of biofuel from triglycerides. The conventional approach for achieving this reaction is transesterification with methanol which releases glycerol as a waste product which must be removed. Conceptually, the hydrogenolysis of the C-C bonds in the glyceride backbone would lead to biodiesel (FAME; Fatty Acid Methyl Esters) in a completely atom-efficient way with no formation of glycerol. Developing a workable strategy for the selective hydrogenolysis of C-C bonds would be a powerful synthetic method but it will be a very tough problem to solve. Its application to biodiesel synthesis would have an incredible impact - biodiesel production in Europe in 2008 was nearly 8 million tonnes!Secondly, I want to develop a new strategy for the synthesis of bidentate ligands, which I am calling metallo-ligands. The core idea is to prepare very simple monodentate phosphines (or other donors) of the general form X-X-PR2 where the X groups are oxygen or nitrogen and the spacer groups would be easily-coupled units which could be enantiomerically pure. One metal, such as magnesium, or perhaps a lanthanide, would bind to the X groups generating a bidentate phosphine without the usual synthetic challenge that this presents. A second metal, such as ruthenium or nickel, would bind to the phosphines and be the catalytic heart of the ensemble. Subtle changes could be made to the bite angle of the phosphine; imagine progression through the lanthanide contraction; imagine changing the geometry of the first metal to switch the conformation of the ligand. The first metal could be a Lewis acid, and with an appropriate spacer, activate a molecule with high regioselectivity at the second metal site. The possibilities for catalysis seem limitless, but it needs time to develop these ideas into practical solutions.