Dream Fellowship. Innovations in Catalysis

这项建议是为了授予一项奖学金，这将使我能够把我的时间全部投入到研究活动中。我有两个主要的领域可以开发，但这个奖学金的另一个特点是，在赠款过程中会出现更多的想法。这将通过参与解决创造性问题的培训来培养创造力来实现。首先，我将调查从甘油三酯制备生物燃料的过程。实现这一反应的传统方法是与甲醇的酯交换反应，这会释放甘油作为废品，必须去除。从概念上讲，甘油酯主链上的C-C键的氢解将以完全原子高效的方式生成生物柴油(FAME；脂肪酸甲酯)，而不会形成甘油。开发一种可行的C-C键选择性氢解策略将是一种强有力的合成方法，但这将是一个非常难以解决的问题。它在生物柴油合成中的应用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，我想开发一种合成双齿配体的新策略，我称之为金属配体。其核心思想是制备非常简单的单齿膦(或其他给体)的一般形式的X-X-PR2，其中X基团是氧或氮，间隔基将是容易偶联的单元，可以是对映体纯度。一种金属，如镁，或者可能是稀土元素，可以与X基团结合，生成双齿磷化氢，而不会出现通常的合成挑战。第二种金属，如Ru或镍，将与磷化氢结合，成为整体的催化核心。可以对磷化氢的咬合角进行微妙的改变；想象通过镧系元素的收缩进行进展；想象改变第一个金属的几何结构来改变配体的构象。第一个金属可以是Lewis酸，并通过适当的间隔物在第二个金属位置激活具有高区域选择性的分子。催化的可能性似乎是无限的，但需要时间将这些想法发展成实际的解决方案。

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.