Synthesis and Study of Cationic Gold pi-Complexes

阳离子金π配合物的合成与研究

• 批准号: 0911265
• 负责人: Ross Widenhoefer
• 金额: $ 43.5万
• 依托单位: Duke University
• 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: 2009-08-15 至 2012-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0911265&HistoricalAwards=false
• 关键词: Synthesis; Study; Cationic; Gold; pi

This project is directed toward the syntheses and study of cationic, 14-electron gold(I) pi-alkene, pi-allene, and pi-alkyne complexes. Cationic gold(I) complexes have recently emerged as effective catalysts for the functionalization of C-C multiple bonds with carbon and heteroatom nucleophiles. However, the cationic, two-coordinate gold(I) pi-complexes germane to catalysis remain scarce and, as a result, little is known about the structure and reactivity of these important complexes. Execution of the proposed research activities will fill this gap in our understanding. Studies directed toward realizing this objective include analysis of 1) the ground-state structure and fluxional behavior of cationic gold(I) pi-complexes, 2) the relative binding ability pi-hydrocarbyl ligands to a cationic gold fragment, 3) the kinetics of degenerative ligand exchange of cationic gold(I) pi-complexes, and 4) the reactivity of gold pi-complexes toward nucleophiles. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Ross Widenhoefer of the Department of Chemistry at Duke University. Professor Widenhoefer's research efforts are directed, in large part, to the mechanistic analysis of the gold(I)-catalyzed addition of carbon and heteroatom nucleophiles to alkenes and allenes. Realization of the proposed activities will provide mechanistic information valuable to the ever-growing global community of researchers working toward the development of new and more efficient gold(I) catalyzed transformations for application in organic synthesis and pharmaceutical development.

本计画系针对阳离子十四电子金（I）π-烯烃、π-联烯及π-炔配合物之合成与研究。 最近出现的阳离子金（I）配合物作为用碳和杂原子亲核试剂官能化C-C多重键的有效催化剂。 然而，阳离子，两个配位的金（I）π-配合物密切相关的催化仍然稀缺，因此，很少有人知道这些重要的配合物的结构和反应性。 执行拟议的研究活动将填补我们认识上的这一空白。 针对实现这一目标的研究包括分析1）阳离子金（I）π-配合物的基态结构和流动行为，2）π-烃基配体与阳离子金片段的相对结合能力，3）阳离子金（I）π-配合物的退化配体交换动力学，以及4）金π-配合物对亲核试剂的反应性。 有了这个奖项，有机和高分子化学计划正在支持杜克大学化学系的Ross Wessenhoefer教授的研究。 Wyndahoefer教授的研究工作在很大程度上是针对金（I）催化的碳和杂原子亲核试剂与烯烃和联烯加成的机理分析。 实现拟议的活动将提供有价值的机制信息，不断增长的全球研究人员社区的工作，朝着新的和更有效的金（I）催化转化的有机合成和药物开发中的应用。