Studies on Electrophilic Metal Complexes in Lewis Acid-Catalyzed C-C Bond-Forming Reactions

在这个合作项目中，将研究阳离子八面体铱（III）配合物在C-C键形成反应中的催化行为。 首先，Nazarov环化反应的机制将进行彻底的调查，使用Ir（III）配合物作为工具，研究在反应中所涉及的步骤的复杂序列。 其次，将开发进行新串联序列的选择性方法和使用刘易斯酸性Ir（III）络合物进行烯醇烷基化的新方法。 最后，手性催化剂的不对称Nazarov环化和多步序列的基础上阳离子Ir（III）系统将被合成和研究，包括新的C2对称配合物密切相关的已知催化剂具有相邻的不稳定的结合位点的催化剂金属中心。有了这个奖项，有机和高分子化学计划支持艾莉森前沿教授和化学系教授理查德艾森伯格在罗切斯特大学的研究合作。 亲电Ir（III）配合物催化研究有助于开发商品和精细化学品制备所需的新合成方法。 通过催化作用增加分子复杂性是创造新的有用化合物的关键手段，这些化合物的潜在影响超出了研究实验室。

In this collaborative project, the catalytic behavior of cationic octahedral iridium(III) complexes will be investigated in C-C bond-forming reactions. First, thorough investigation of the mechanism of Nazarov cyclization will be conducted, using Ir(III) complexes as a tool to study the complex sequence of steps involved in the reaction. Second, selective methods to conduct new tandem sequences and new methods for enol alkylation using Lewis acidic Ir(III) complexes will be developed. Finally, chiral catalysts for asymmetric Nazarov cyclizations and multi-step sequences based on cationic Ir(III) systems will be synthesized and studied, including new C2 symmetric complexes closely related to the known catalysts possessing adjacent labile binding sites on the catalyst metal center. With this award, the Organic and Macromolecular Chemistry Program is supporting the research collaboration of Professor Alison Frontier and Professor Richard Eisenberg of the Department of Chemistry at the University of Rochester. Research in the catalysis of electrophilic Ir(III) complexes aids in the development of new synthetic methodologies needed for the preparation of commodity and fine chemicals. Increasing molecular complexity through catalysis represents a key means of creating new useful compounds of potential impact beyond the research laboratory.