Development of Catalysts for Asymmetric Reactions and Energy Conversion.

药品的有效生产和可再生能源的储存/转化是现代化学研究的基本和重要目标。我们的第一个项目建立在我们发现一种高效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基氢化物。这些可燃的氢化物必须运输，它们的使用需要危险的放热水解，产生废物。催化酰胺氢化消除了这些负面影响，制药公司已经确定了这种反应的发展是降低成本和药物生产对环境影响的关键需求。我们最近发现Ru(Ph2PCH2CH2NH2)2(H)2,(1)是一种强大的酰胺加氢催化剂，其活性比以前的催化剂高67倍以上。化合物1氢化了多种用途广泛的酰胺，产率高，催化剂用量少。这些氢化反应与C-N裂解一起产生产物醇和胺。它们还需要额外的基础，这可能是一个限制。我们最近开发了一种不加碱的催化剂。我们将首先修改这种重要的催化剂，使其活性最大化，并使其足够稳定，便于长期储存。我们目前正在开发不对称版本的酰胺氢化反应，其进行速率高达99% ee。外消旋酰胺可以在非常温和的条件下（4atm H2，室温）以动态动力学分辨率（DKR）加氢。我们将使用相同的方法开发外消旋酯的DKR还原。目前，在文献中只有一个这种重要类型的氢化的例子，它是在低选择性和不切实际的催化剂负载下进行的。研究了外消旋酰胺C-O裂解的不对称DKR加氢反应。我们已经有了很有希望的早期结果，我们将在此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，该催化剂是迄今为止在流动反应器中用于不对称酮加氢、烯烃环异构化和烯烃加氢的最可重复使用的催化剂。该系统已获得加拿大绿色中心的许可，我们正在与默克和Dr. Reddy's合作开发定制聚合催化剂。我们建议开发一种新型聚合催化剂，使酯类和酰胺类在流动反应器中连续加氢。我们还将为这些催化剂开发磁性支架，以便使用简单的磁铁将它们隔离以重复使用。***在我们的第三个项目中，我们开发了一种简单的，迄今为止已知的最活跃的水氧化催化剂的台式合成。我们将开发这些催化剂，研究它们是如何运作的，并在原型水电解槽中对它们进行评估，作为高效太阳能储能系统的一部分

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.**