Synthesis and study of potential intermediates in gold(I) pi-activation catalysis

金(I)π活化催化潜在中间体的合成与研究

• 批准号: 1213957
• 负责人: Ross Widenhoefer
• 金额: $ 45.6万
• 依托单位: Duke University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-08-01 至 2015-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1213957&HistoricalAwards=false
• 关键词: Synthesis; study; potential; intermediates; gold

In this project funded by the Chemical Synthesis Program of the Chemistry Division, Professor Ross A. Widenhoefer of the Department of Chemistry at Duke University will explore the synthesis and study of potential intermediates in gold(I) pi-activation catalysis, including pi-alkene, pi-allene, and sigma-vinyl complexes. An understanding of the mechanisms of gold pi-activation catalysis has lagged significantly behind the synthetic development of this chemistry, and available information is largely derived from computational analyses. As such, little experimental information is available regarding the behavior of gold pi- and sigma-complexes generated as intermediates in gold(I)-catalyzed hydrofunctionalization and likewise, experimental information regarding the structure and reactivity of cationic gold carbene complexes germane to gold-catalyzed alkene cyclopropanation and enyne cycloaddition is lacking. The proposed research activities aim to fill these gaps and to develop an experimentally-grounded understanding of the mechanisms of gold pi-activation catalysis.The emergence of cationic gold(I) complexes as catalysts for the functionalization of carbon carbon multiple bonds (pi-activation catalysis) represents one of the most important developments in homogenous catalysis over the past decade. These transformations often display high efficiency, excellent atom economy, and high regio- and stereoselectivity, making them particularly attractive for application in both target-oriented synthesis and pharmaceutical development. The research activities undertaken in this project will provide mechanistic information that will facilitate the continued development of this important family of synthetic transformations. In addition, the research activities related to this project are fully integrated with the scientific education and training of the graduate and undergraduate research participants including students from ethnic groups traditionally underrepresented in the sciences.

在化学司化学合成计划资助的该项目中，杜克大学化学系的罗斯·A·维登霍夫教授将探讨黄金（I）PI-Activation催化中潜在中间体的综合和研究，包括Pi-Alceene，Pi-Altalene，Pi-Allene，Pi-Allene，Pi-Allene和Sigma-Vinyl Complexs。 对黄金PI-Activation催化机制的理解已显着落后于该化学的合成发展，并且可用信息主要来自计算分析。 因此，几乎几乎没有关于在黄金（I）中产生的金型和sigma-complexes的行为的实验信息（i）（i）催化的加氢功能化以及同样的，同样的，有关阳离子金碳烯基酸酯的结构和反应性的实验信息，将其与黄金烯烃环化的烯烃环化和反应性的结构和反应性相结合。 拟议的研究活动旨在填补这些空白，并对黄金Pi-Activation催化的机制进行实验基础的理解。作为碳碳多键（PI-Activation催化）功能化阳离子黄金（I）复合物的出现，是在猫科动物中最重要的发展。 这些转变通常表现出很高的效率，出色的原子经济以及高区域和立体选择性，这使得它们对于在目标综合和药物开发中的应用中特别有吸引力。 该项目中进行的研究活动将提供机械信息，以促进这一重要的合成转型家族的持续发展。 此外，与该项目相关的研究活动与研究生和本科研究参与者的科学教育和培训完全融合在一起，包括传统上在科学中人数不足的族裔学生。