Early transition metal and lanthanide amidate complexes: modular, easily accessed complexes for catalysis

早期过渡金属，如钛和锆，以及稀土金属，已经成功地用于金属介导的有机合成。作为催化剂，这些金属能够促进通常不能发生的反应。金属催化对于工业应用非常重要，因为它以经济有效、能源高效的方式促进化学转化，同时最大限度地减少化学废物。当然，催化是发展环境友好的绿色化学和可持续的化学生产方法的关键。早期过渡金属和稀土金属特别适合大规模应用，因为它们成本低，毒性低。对于容易制备的，我们的研究组开发的廉价催化络合物在制药、聚合物和精细化学工业中显示出广泛的重要催化转化的前景。在使用上述金属类别的基础上，我们开发了一系列在分子内反应的选择性C-N键形成方面表现出前所未有的和非常理想的催化活性的络合物(酰胺化络合物)(两个反应伙伴都包含在一个起始材料中)。我们建议继续探索这些络合物的C-N键形成，以实现化学合成中的一个长期目标，以分子间方式将胺(N-H键)加成到简单的烯烃(C=C键)上(反应伙伴是两个独立的分子)。除了选择性地形成C-N键外，我们还将探索这一新的络合物家族在C-C偶联反应以及聚合反应中的潜在应用。最近的结果表明，这些络合物在催化制备可生物降解的、可堆肥的聚合物方面是有用的。所需资金将支持我们继续努力充分探索和开发这些新的催化体系。

Early transition metals, such as titanium and zirconium, and lanthanide metals have been used successfully for metal-mediated organic synthesis.  As catalysts, these metals are able to promote reactions that normally cannot occur.  Catalysis is very important for industrial applications, as it promotes chemical tranformations in a cost effective, energy efficient manner while minimizing chemical waste.  Certainly catalysis is key to the development of environmentally friendly green chemistry and sustainable methods for chemical production.  Early transition and lanthanide metals are particularly attractive for large scale applications, due to the fact that they are of low cost and low toxicity.  The easily prepared, inexpensive catalytic complexes developed in our research group show promise for a broad range of important catalytic transformations in the pharmaceutical, polymer and fine chemical industries.  Using the class of metals presented above, we have developed a family of complexes (amidate complexes) that display unprecedented and highly desirable catalytic activity in selective C-N bond formation for intramolecular reactions (both reactive partners are contained in one starting material).  We propose to continue our exploration of these complexes for C-N bond formation, to achieve a long-standing goal in chemical synthesis, the addition of amines (N-H bonds) to simple alkenes (C=C bonds) in an intermolecular fashion (reactive partners are two separate molecules).    In addition to selective C-N bond formation we will be exploring the potential application of this new family of complexes in C-C coupling reactions, as well as polymerization reactions.  Recent results demonstrate the usefulness of these complexes in the catalytic preparation of biodegradable, compostable polymers.The funds requested will support our on-going efforts to fully explore and develop these new catalytic systems.