Studies on the Use of Cationic Iridium(III) Complexes in Lewis Acid-Catalyzed C-C Bond-Forming Reactions

阳离子铱(III)配合物在路易斯酸催化C-C键形成反应中的应用研究

• 批准号: 0556225
• 负责人: Richard Eisenberg
• 金额: $ 24.08万
• 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: 2006
• 资助国家: 美国
• 起止时间: 2006-04-15 至 2009-03-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0556225&HistoricalAwards=false
• 关键词: Studies; Use; Cationic; Iridium; III

In this project, the catalytic behavior of cationic octahedral iridium(III) d6 complexes will be studied for C-C bond formation in reactions principally involving the Nazarov cyclization. The kinetics and mechanism of Nazarov cyclization catalyzed by cationic Ir(III) complexes having adjacent labile binding sites will be studied, including a detailed examination of substrate binding coupled with targeted substrate variation to probe Lewis acidity and ligand modification to assess electronic and steric effects on catalyst effectiveness. The Ir(III) complexes will be exploited as catalysts for tandem or cascade reaction sequences initiated with Nazarov cyclization to create complex carbocyclic systems with multiple stereocenters in single pot procedures. Chiral Ir(III) catalysts with labile adjacent sites will be developed for both asymmetric Nazarov cyclization and tandem reactions.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Richard Eisenberg and Dr. Alison J. Frontier, of the Department of Chemistry at the University of Rochester. In the development of synthetic methods for the construction of complex organic molecules including natural products and pharmaceutically active compounds, catalysis remains at the forefront. This project represents a new collaboration between an inorganic chemist whose main research focus has been on bond activation and catalysis using platinum group elements and an organic chemist whose research program extends from synthetic methodology development using organometallic compounds to the total synthesis of natural products. Drs. Eisenberg and Frontier will explore the fundamental mechanisms by which particular iridium-catalyzed reactions proceed, with the resulting information allowing them to develop more highly controlled reactions. These studies will in turn permit the development of new synthetic methodologies applicable to the synthesis of commodity and fine chemicals.

在本项目中，将研究阳离子八面体铱（III）d 6配合物在主要涉及Nazarov环化反应的C-C键形成中的催化行为。Nazarov环化催化的动力学和机制的阳离子Ir（III）配合物具有相邻的不稳定的结合位点将进行研究，包括一个详细的检查与有针对性的基板的变化，探针刘易斯酸性和配体修饰，以评估电子和空间效应的催化剂的有效性。Ir（III）配合物将被利用作为催化剂的串联或级联反应序列与Nazarov环化引发的单锅程序中创建复杂的碳环系统与多个立体中心。手性Ir（III）催化剂与不稳定的相邻位点将开发用于不对称Nazarov环化和串联反应。有了这个奖项，有机和大分子化学计划是支持博士理查德·艾森伯格和博士艾莉森J.前沿，化学系在罗切斯特大学的研究。在构建复杂有机分子（包括天然产物和药物活性化合物）的合成方法的开发中，催化仍然处于最前沿。该项目代表了无机化学家之间的新合作，其主要研究重点是使用铂族元素的键活化和催化，以及有机化学家，其研究计划从使用有机金属化合物的合成方法开发延伸到天然产物的全合成。Eisenberg博士和Frontier博士将探索特定铱催化反应进行的基本机制，由此产生的信息使他们能够开发更高度受控的反应。这些研究反过来将有助于开发适用于商品和精细化学品合成的新合成方法。