Development of Catalysts for Asymmetric Reactions and Energy Conversion.

高效生产药物和储存/转化可再生能源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有效的酰胺加氢催化剂的基础上。在工业中酰胺的还原通常利用化学计量的主族取代基。这些易燃物必须运输，其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求。我们最近发现Ru（Ph 2 PCH 2CH 2NH 2）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以高产率和低催化剂载量氢化多种有用的酰胺。这些氢化伴随C-N裂解进行以产生产物醇和胺。它们还需要添加碱，这可能是一个限制。我们最近开发了一种催化剂，它不需要添加碱。我们将开始对这种重要的催化剂进行改性，使其活性最大化，并使其足够稳定，便于长期储存。我们目前正在开发酰胺氢化的不对称版本，其进行高达99%ee。外消旋酰胺可以在极其温和的条件下（4 atm H2，室温）用动态动力学拆分（DKR）氢化。我们将使用相同的方法开发外消旋酯的DKR还原。目前，在文献中只有这种重要类型的氢化的一个实例，并且它以低选择性和不切实际的催化剂负载进行。我们将发展外消旋酰胺的不对称DKR氢化和C-O裂解。我们已经取得了令人鼓舞的早期成果，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，这些催化剂是迄今为止最可重复使用的，用于流动反应器中的不对称酮氢化、烯烃环化异构化和烯烃氢化。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开发定制的聚合催化剂。我们建议开发新的高分子催化剂，连续酯化和酰胺在流动反应器。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重新使用。* 在我们的第三个项目中，我们开发了一种迄今为止已知的最具活性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，研究它们的工作原理，并在原型水电解槽中对其进行评估，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.**