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

路易斯酸催化C-C键形成反应中亲电金属配合物的研究

• 批准号: 0847851
• 负责人: Alison Frontier
• 金额: $ 41万
• 依托单位: University of Rochester
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-02-01 至 2012-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0847851&HistoricalAwards=false
• 关键词: Studies; Electrophilic; Metal; Complexes; Lewis

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.

在这个合作项目中，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将被研究。首先，深入研究纳扎罗夫环化的机理，以Ir（III）配合物为工具，研究该反应所涉及的复杂步骤序列。其次，将开发利用Lewis酸性Ir（III）配合物进行新型串联序列的选择性方法和烯醇烷基化的新方法。最后，将合成和研究不对称Nazarov环化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新的C2对称配合物，这些催化剂在催化剂金属中心具有邻近的不稳定结合位点。通过这个奖项，有机和大分子化学项目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。研究亲电Ir（III）配合物的催化作用有助于开发新的合成方法，以制备商品和精细化学品。通过催化作用增加分子复杂性是在研究实验室之外创造具有潜在影响的新有用化合物的关键手段。