Abundant transition metals in catalysis

我们的项目将侧重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便宜、对人类健康更无害、更适合绿色化学过程的更丰富的金属取代基于贵重稀有铂族金属的催化剂。我们的催化剂将允许有效和新的胺合成在制药、农用化学品和聚合物中具有重要意义，以及在制药、香水和绿色能源储存中应用的醇。在过去的五年中，我们开发了最先进的催化剂（FeATHerII和FeATHerIII催化剂），用于酮类和某些亚胺的不对称转移氢化（ATH），以及最近使用铁和锰进行酮类的不对称压力氢化。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（明斯特大学），以及访客和本科生组成了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，更活跃、更高效、更有选择性，并且在氧和失活途径方面更稳健。与酶一样，我们的催化剂将在配体上设计与亚胺和酮互补的基团，以显著提高对制药和精细化工行业有价值的醇和胺生产的催化对映选择性。我们将利用我们在配体合成和计算建模方面的技能，使用既定的方法建立氢键供体和受体。我们的膦醛前体是这种化学反应的理想起点。这些新型金属配合物将应用于有机合成中各种重要的不对称反应，包括硅氢化、硼氢化和碳碳键形成。最近的一个特点是使用与伯胺或仲胺相连的n -杂环碳烯给体（例如，由研究生Kai Wan发现的对映纯Kaibene），可以真正提高活性。***我们在2014年首次描述的用于预测氢化物和二氢配合物酸度的配体酸度常数（LAC）方程对催化剂设计具有重要意义。用于探索和指导耐酸性条件下二氧化碳还原为液体燃料和亚胺加氢催化剂的合成。我们将测量顺磁性金属氢化物配合物的酸度，并使用最先进的计算工具来了解决定其酸度的因素。为了协助催化碳氢键功能化的热门领域，我们将在实验和计算上扩展LAC的概念，以协调（agostic）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.**