Applications of Cyclopropenylidene Metal Complexes and Thioureas in Catalysis

我们的研究项目结合了有机合成、计算和物理有机化学，旨在改进催化过程和开发新的过程。这些活动提供了对化学反应、分子结构和成键的机械洞察。促进这种兴趣的是催化在生产具有重要医学价值的天然和非天然化合物、聚合物、精细化学品等大宗材料以及来自化石和可再生燃料来源的能源方面的广泛使用，同时推进更高效和更绿色的制造工艺，以保护日益减少的资源和保护环境。在未来五年，我们的计划将重点放在以下几个方面： (1)我们将开发从硬币金属(铜、银、金)衍生的络合物，并将其应用于各种有用的化学产品。特别令人感兴趣的是，这些配合物将在反应中使用，提供小环中原子的独特排列，激活非常不愿反应的化学键，以及合成杂环化合物。我们预计这些化合物将表现出许多有趣的化学性质，我们将通过理论和光谱技术的结合来研究这些性质。 (2)我们将开发基于硫脲的氢键催化剂，用于糖的合成，包括C-糖苷，这是许多抗肿瘤、抗生素和抗糖尿病(II)药物中的关键基序化合物。C-糖苷是糖的类似物，与单个原子的存在不同，它的合成具有重要意义，因为它们对细胞组织中的新陈代谢和特定功能具有稳定性。由于C-糖苷在患者的血液和组织中持续时间更长，它们在新药设计中很有用。我们预计这一发现领域将产生直接适用于催化、基本化学知识和药物开发的深远结果。 除了对反应机理和化学键的基本认识外，拟议的研究成果还将推动有机合成、催化和材料科学领域的发展。我们的一系列金属络合物和硫脲氢键催化剂的进步将使新的催化模式成为可能，从而为合成复杂的天然产品、药物目标和增值化学品提供有效的合成路线。这项研究还将为制药行业和学术界未来的化学专业人员提供良好的培训。

Our research program combines organic synthesis, computational, and physical organic chemistry directed at the improvement of catalytic processes and the development of new ones. These activities provide mechanistic insight into chemical reactivity, molecular structure, and bonding. Fueling this interest is the widespread use of catalysis in the production of medicinally important natural and unnatural compounds, bulk materials such as polymers, fine chemicals, and energy from both fossil and renewable fuel sources, while advancing more efficient and green manufacturing processes to preserve diminishing resources and protect the environment. Over the next five years our program will focus on the following: (1) We will develop complexes derived from coinage metals (copper, silver, gold) and apply these to a broad spectrum of useful chemical products. Of specific interest will be the use of these complexes in reactions providing unique arrangements of atoms in small rings, activation of chemical bonds that are very reticent to react, and the synthesis of heterocyclic compounds. We anticipate that these complexes will exhibit a number of interesting chemical properties, which we will investigate through the combination of theoretical and spectroscopic techniques. (2) We will develop thiourea-based hydrogen bond catalyst that will be applied to the synthesis of sugars, including C-glycosides, compounds from nature that serve as key motifs in numerous antitumor, antibiotic, and antidiabetic (type II) agents. The synthesis of C-glycosides, which are sugar analogs differing by the subtle presence of a single atom, is of importance because of their stability to metabolism and specific function in cellular tissues. Because C-glycosides last longer in the blood and tissues of patients, they are useful in the design of new drugs. We project this area of discovery will have far-reaching outcomes directly applicable to catalysis, basic chemical understanding, and drug development. In addition to fundamental insight into reaction mechanisms and chemical bonding, the outcome of the proposed research will advance the fields of organic synthesis, catalysis, and material science. Our advancement of an array of metal complexes and thiourea hydrogen bond catalysts will enable new modes of catalysis allowing for efficient synthetic routes to complex natural products, pharmaceutical targets, and value-added chemicals. This research will also provide excellent training for future chemistry professionals both in the pharmaceutical industry and in academia.