Development of Catalysts for Asymmetric Reactions and Energy Conversion.

药物的高效生产和可再生能源的储存/转化是现代化学研究的基本、至关重要的目标。我们的第一个项目建立在我们发现了一种高效的酰胺加氢催化剂的基础上。在工业中，酰胺的还原通常使用化学计量主族氢化物。这些易燃氢化物必须运输，使用它们需要危险的、放热的水解过程，从而产生废物。催化酰胺加氢消除了这些负面影响，Pharma公司已将这种反应的开发确定为降低制药生产成本和环境影响的关键需要。我们最近发现，Ru(Ph_2PCH_2CH_2N_2)_2(H)_2，(1)是一种高效的酰胺加氢催化剂，其催化活性是以往催化剂的67倍以上。化合物1氢化多种有用的酰胺类化合物，产率高，催化剂用量少。这些加氢反应通过C-N裂解生成醇和胺。它们还需要增加基数，这可能是一个限制。我们最近开发了一种催化剂，无需添加碱即可运行。我们将首先对这种重要的催化剂进行修饰，以最大限度地提高其活性，并使其足够稳定，以便长期储存。我们目前正在开发不对称形式的酰胺氢化，可在高达99%的ee中进行。外消旋酰胺可以在非常温和的条件下(4atmH2，室温)用动态动力学拆分(DKR)进行氢化。我们将使用相同的方法开发外消旋酯的DKR还原。目前，这种重要类型的加氢反应在文献中只有一个例子，而且选择性低，催化剂负载不切实际。我们将开发具有C-O裂解的外消旋酰胺的不对称DKR氢化反应。我们已经有了有希望的初步成果，我们将在这些成果的基础上发展这一重要的、前所未有的反应。 第二个项目建立在我们开发的聚合手性催化剂的基础上，这些催化剂是迄今为止最可重复使用的流动反应器中不对称酮加氢、烯烃环异构化和烯烃加氢的催化剂。该系统已获得加拿大绿色中心的许可，我们正在与默克和雷迪博士合作开发定制聚合催化剂。我们建议开发新的聚合物催化剂，在流动反应器中连续加氢酯和酰胺。我们还将为这些催化剂开发磁性载体，以便可以使用简单的磁铁将它们分离出来，以便重复使用。 在我们的第三个项目中，我们开发了一种迄今为止最活跃的水氧化催化剂的简单台式合成方法。我们将开发这些催化剂，研究它们是如何运行的，并在作为高效太阳能存储系统一部分的原型水电解槽中对它们进行评估。

The efficient production of pharmaceuticals and the storage/transformation of energy from renewable sources are fundamental, vital objectives of modern chemical research. Our first project builds on our discovery of an efficient amide hydrogenation catalyst. The reduction of amides in industry typically utilizes stoichiometric main-group hydrides. These flammable hydrides must be transported, and their use requires a dangerous, exothermic hydrolysis that generates waste. Catalytic amide hydrogenation eliminates these negatives, and Pharma has identified the development of such a reaction as a key need to reduce the costs and environmental impact of pharmaceutical production. We recently discovered that Ru(Ph2PCH2CH2NH2)2(H)2, (1) is a powerful amide hydrogenation catalyst that is over 67x more active than previous catalysts. Compound 1 hydrogenates a wide, useful variety of amides with high yields and low catalyst loadings. These hydrogenations proceed with C-N cleavage to generate the product alcohol and amine. They also require added base, which can be a limitation. We very recently developed a catalyst that operates without added base. We will begin by modifying this important catalyst to maximize its activity and to make it stable enough for convenient storage over long periods of time. We are currently developing asymmetric versions of amide hydrogenations that proceed in up to 99 % ee. Racemic amides can be hydrogenated with dynamic kinetic resolution (DKR) under extremely mild conditions (4 atm H2, room temperature). We will develop DKR reductions of racemic esters using the same methodology. Currently, there is only one example of this important type of hydrogenation in the literature, and it proceeded with low selectivity and impractical catalyst loadings. We will develop the asymmetric DKR hydrogenation of racemic amides with C-O cleavage. We already have promising early results that we will build upon to develop this important unprecedented reaction. The second project builds upon our development of polymerized chiral catalysts that are the most reusable to date for asymmetric ketone hydrogenations, olefin cycloisomerizations, and olefin hydrogenations in flow reactors. This system has been licensed by GreenCentre Canada and we are developing custom polymerized catalysts with Merck and Dr. Reddy's. We propose to develop new polymeric catalysts that hydrogenate esters and amides continuously in flow reactors. We will also develop magnetic supports for these catalysts so that simple magnets can be used to isolate them for reuse. In our third project, we have developed a simple, bench-top synthesis of the most active water oxidation catalysts known to date. We will develop these catalysts, investigate how they operate, and evaluate them in prototype water electrolyzers as part of highly efficient solar energy storage systems.