Abundant transition metals in catalysis

我们的计划将专注于发现基于可持续金属锰、钴和铁的新催化剂。工业正在努力用这些更丰富的金属取代以贵重和稀有的铂族金属为基础的催化剂，这些金属更便宜，对人类健康更有利，更适合绿色化工过程。我们的催化剂将使在制造药品、农用化学品和聚合物以及在制药、香水和绿色能源存储中应用的醇的重要的胺的有效和新的合成成为可能。在过去的五年里，我们开发了最先进的催化剂(FeATHerII和FeATHerIII催化剂)，用于酮和某些亚胺的不对称转移氢化(ATH)，最近还用于使用铁和锰的酮的不对称加压氢化。随着这一成功，我的研究团队已经发展到11名研究生，8名国内学生和3名共同指导(U·明斯特)，以及来访者和本科生-一个强大的催化剂发现团队。*我们将使用我们成熟的实验和计算方法来发现新的催化剂，这些催化剂更容易、更安全地合成，更具活性，更有选择性，在氧气和失活路线方面也更坚固。与酶一样，我们的催化剂将在配体上与亚胺和酮的配体上具有互补基团，以显著提高生产对制药和精细化工有价值的醇和胺的催化对映体选择性。我们将利用我们在配体合成和计算建模方面的技能，使用现有的方法建立氢键供体和受体。我们的膦醛前驱体是这种化学的理想起点。这些新的金属络合物将应用于有机合成中的各种重要的不对称反应，包括硅氢化、硼氢化和碳碳键的形成。最近的一个特点是使用N-杂环卡宾供体与伯胺或仲胺(例如研究生万凯发现的对映体凯宾)捆绑在一起，提供真正的活性提升。*我们的配体酸度常数(LAC)方程于2014年首次描述，用于预测氢化物和二氢络合物的酸度，该方程对催化剂设计具有重要意义。它将用于探索和指导耐二氧化碳还原为液体燃料和亚胺加氢的酸性条件下的催化剂的合成。我们将测量顺磁性金属氢化物络合物的酸度，并使用最先进的计算工具来了解决定它们酸度的因素。为了在催化碳氢键功能化这一热点领域提供帮助，我们将从实验和计算两方面将LAC概念扩展到配位(无配位)碳氢键。

Our program will focus on the discovery of new catalysts based on the sustainable metals manganese, cobalt and iron. Industry is striving to replace catalysts based on platinum group metals that are precious and rare with these more abundant metals that are cheaper, more benign to human health and more appropriate for green chemical processes. Our catalysts will allow effective and new syntheses of amines of importance in making pharmaceuticals, agrochemicals and polymers, and alcohols with applications in pharma, fragrances and green energy storage. In the past five years we developed state-of-the-art catalysts (the FeATHerII and FeATHerIII catalysts) for asymmetric transfer hydrogenation (ATH) of ketones and certain imines, and more recently for the asymmetric pressure hydrogenation of ketones using iron and manganese. With this success, my research team has grown to eleven graduate students, 8 domestic and 3 co-supervised (U. Muenster), along with visitors and undergraduates – a powerful catalyst discovery team. *** We will use our proven experimental and computational approaches to discover new catalysts that are easier and safer to synthesize, more active, productive and selective and more robust with respect to oxygen and deactivation routes. Like enzymes, our catalysts will be designed with complementary groups on the ligand to those of imines and ketones to dramatically improve catalytic enantioselectivity in the production of alcohols and amines of value to the pharmaceutical and fine chemical industries. We will use our skill in ligand synthesis and computational modelling to build in hydrogen bond donors and acceptors using established methods. Our phosphine aldehyde precursors are an ideal starting point for this chemistry. These new metal complexes will be applied to a variety of important asymmetric reactions in organic synthesis including hydrosilylation, hydroboration and carbon-carbon bond forming. A more recent feature is the use of N-heterocyclic carbene donors tethered with primary or secondary amines (e.g. enantiopure Kaibene discovered by graduate student Kai Wan) that provide a real boost in activity. *** Our ligand acidity constant (LAC) equation that was first described in 2014 for predicting the acidity of hydride and dihydrogen complexes has significant implications for catalyst design. It will be used to explore and guide the synthesis of catalysts that are tolerant to the acidic conditions of carbon dioxide reduction to liquid fuels and imine hydrogenation. We will measure the acidity of paramagnetic metal hydride complexes and use state of the art computational tools to understand the factors that determine their acidity. To assist in the hot field of catalytic carbon-hydrogen bond functionalization we will extend the LAC concepts both experimentally and computationally to coordinated (agostic) carbon-hydrogen bonds.**