New organometallic and coordination chemistry for the formation and activation of carbon-carbon bonds

过渡金属有机金属化学在化学技术的许多领域中起着关键作用。 金属介导的有机反应提供了许多用于商品和精细化学品的开发和商业生产的方法，在所有依赖有机合成和催化的行业中-制药，农业化学品，聚合物和结构材料。 拟议的研究计划是跨学科的，结合无机和有机化学来理解和操纵过渡金属有机金属反应性和功能的原则。 我们的方法可以被描述为分子水平上的工程：合理设计和实施新的金属介导的有机反应，包括化学计量和催化。 我们的计划影响基础化学和实际应用，推进我们对有机金属反应机制的理解，并将新的转化引入有机合成和催化。 该计划提供了一个独特的智力环境，培养创造性和生产力的年轻科学家，有必要解决严重的研究问题的命令和信心。 提出了四个具体的调查，从新的催化剂设计到强碳-碳键的受控裂解的新策略。 首先，新的几何约束的配位络合物将被创建并用于催化，其中金属处于应变配位几何结构中。 其他三个项目涉及创造新的反应，其中复杂的有机分子是在一个高度控制的方式。 第一个扩展的调查金属导向的自由基烷基化，利用金属配位反转自然选择性。 在第二个项目中，将开发新的金属介导的环加成反应，用于制备重要的碳环和杂环材料。 第三个项目的重点是新的金属定向扩环反应，这是一个不寻常的过程，在这个过程中，金属裂开一个碳-碳键，插入一个新的两碳单元。

Transition metal organometallic chemistry plays a critical role in many sectors of chemical technology. Metal-mediated organic reactions provide much of the methodology used for the development and commercial production of commodity and fine chemicals, in all industries dependent on organic synthesis and catalysis - pharmaceuticals, agricultural chemicals, polymers, and structural materials. The proposed research program is interdisciplinary, combining inorganic and organic chemistry to understand and manipulate the principles governing transition metal organometallic reactivity and function. Our approach might be described as engineering on a molecular level: the rational design and implementation of new metal-mediated organic reactions, both stoichiometric and catalytic. Our program impacts fundamental chemistry and practical applications, advancing our understanding of organometallic reaction mechanisms and introducing new transformations into organic synthesis and catalysis. This program provides a unique intellectual environment for training creative and productive young scientists, with the command and confidence necessary to solve serious research problems. Four specific investigations are proposed, ranging from new catalyst design to new strategies for the controlled cleavage of strong carbon-carbon bonds. First, new geometrically-constrained coordination complexes will be created and exploited for catalysis, with the metal(s) in strained coordination geometries. The three other projects involve the creation of new reactions in which complex organic molecules are made in a highly controlled fashion. The first expands on investigation of metal-directed radical alkylation, using metal coordination to invert natural selectivities. In the second project, new metal-mediated cycloaddition reactions will be developed for the preparation of important carbocyclic and heterocyclic materials. The third project is focused on new metal-directed ring-expansion reactions, an unusual process in which the metal cleaves open a carbon-carbon bond and inserts in a new two-carbon unit.