Mechanistic Investigations of Nickel-Promoted C-Heteroatom Bond Making Reactions

现代化学工业对我们生活的影响在许多方面都令人叹为观止。有一句谚语说：“世界上有什么不是化学？！”反映了这样一个事实，或多或少，我们周围的每一件可触摸的“东西”(医药和农产品、油漆、油类、粘合剂、塑料和其他材料等)是以这样或那样的方式通过化学创造出来的。除了化学对现代生活和生产“事物”的实际贡献外，化学科学的概念和理论以多种复杂的方式丰富了我们对宇宙、创造、进化和生命本身的理解。事实上，化学有助于理解宇宙，从原子和分子水平开始，再到大宗物质和生命中更大的大分子，最后是行星和恒星。因此，有这样一句话：化学，核心科学。这项提议描述了一个研究计划，致力于研究化学反应的子集，这些化学反应告诉我们化学键是如何形成和断裂的。然后将这些知识付诸实践，以制定高效和对环境无害的方法来合成所谓的有机化学品，这些化学品在化学工业的不同部门，从制药到农用化学品等都有用途。更具体地说，我们建议仔细研究被称为“配体”的化学实体与金属原子的相互作用，这些原子能够促进和控制各种基本反应，这些反应将定义成键和断裂步骤。这项研究的重点将是地球上富含的过渡金属镍，它将与各种配体结合，得到作为稳定但活性预催化剂的“络合物”。我们研究计划的长期目标将包括为所谓的C-H键和烯烃的胺化设计路线。在这些过程中，化学家将丰富的和不太“功能性”(不太有用)的碳基材料转化为新的分子和材料，这些分子和材料具有氮和氧等所谓的杂原子，为原始材料提供了无限的新特性和功能。我们实现这一目标的战略是建立在我们之前研究期间所做发现的基础上。因此，我们在C-H功能化计划的第一步取得的概念上的进展，即相当惰性的C-H键的激活，将使我们能够专注于手头的下一项任务，即将环金属物种转化为具有新形成的C-杂原子键的产品。这将使我们能够确定促进C-H键转化为功能材料和产品的条件和变量。同样，我们将利用我们之前的发现来开发将烯烃转化为更有价值的胺的新方法。

The impact of modern chemical industry on our lives is breath-taking in many respects. The adage, "What in the World Isn't Chemistry?!" reflects the fact that more or less every touchable "thing" around us (pharmaceutical and agricultural products, paints, oils, adhesives, plastics and other materials, etc.) was created, in one way or another, through chemistry. And beyond the practical contributions of chemistry to modern life and producing "things", the concepts and theories of the chemical sciences have enriched our understanding of the universe, creation, evolution, and life itself in multiple and complex ways. Indeed, chemistry helps makes sense of the universe, starting at the atomic and molecular levels, and going on to bulk matter and larger macromolecules of life, and finally to the planets and stars. Hence, the expression: Chemistry, the central science. This proposal describes a research program devoted to investigating a subset of chemical reactions that teach us how chemical bonds are formed and broken. This knowledge is then put into practice to elaborate efficient and environmentally benign methodologies for the synthesis of so-called organic chemicals that have uses in different sectors of the chemical industry, from pharmaceuticals to agrochemicals and beyond. More specifically, we propose to closely examine the interactions of chemical entities called "ligands" with metal atoms that are capable of promoting and controlling various elementary reactions that define bond making and breaking steps. The focus of this study will be the earth-abundant transition metal nickel, which will be combined with various ligands to give "complexes" that act as stable yet reactive pre-catalysts. The long-term objectives of our research program include devising routes for the so-called "functionalization" of C-H bonds and amination of olefins. These are processes whereby chemists convert abundant and less "functional" (less useful) carbon-based materials into new molecules and materials featuring so-called heteroatoms such as nitrogen and oxygen that offer an infinite set of new properties and functions to the original material. Our strategy for achieving this goal is to build on the discoveries made during our previous research studies. Thus, the conceptual advances we have registered on the first step of the C-H functionalization program, i.e., the activation of the fairly inert C-H bonds will allow us to focus on the next task at hand, i.e., the conversion of cyclometallated species into products featuring newly formed C-heteroatom linkages. This would then enable us to define the conditions and variables that facilitate the conversion of C-H bonds into functional materials and products. Similarly, we would use our previous findings to develop new ways for conversion of olefins into more valuable amines.