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Ir(III)配合物在C-C成键反应中的催化行为。首先，将深入研究纳扎罗夫环化反应的机理，使用Ir(III)络合物作为工具来研究反应中涉及的复杂步骤序列。第二，将开发选择性的方法来进行新的串联序列和使用Lewis酸性Ir(III)配合物进行烯醇烷基化的新方法。最后，合成和研究了用于不对称纳扎罗夫环化反应的手性催化剂和基于阳离子Ir(III)体系的多步序列，包括与已知催化剂密切相关的C2对称配合物，这些催化剂在催化剂的金属中心具有相邻的不稳定结合位。通过这一奖项，有机和高分子化学计划支持罗切斯特大学化学系的Alison Frontier教授和Richard Eisenberg教授的研究合作。亲电Ir(III)络合物催化作用的研究有助于开发制备商品和精细化学品所需的新的合成方法。通过催化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的范围。

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.