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.

本研究由化学系化学合成项目资助，Ross A.杜克大学化学系的Wavehoefer将探索金（I）π-活化催化中潜在中间体的合成和研究，包括π-烯烃，π-联烯和σ-乙烯基络合物。 对金π-活化催化机制的理解已经明显落后于这种化学的合成发展，并且可用的信息主要来自计算分析。 因此，关于作为金（I）催化的氢官能化中的中间体产生的金π-和σ-络合物的行为的实验信息很少，并且同样地，缺乏关于阳离子金卡宾络合物锗烷对金催化的烯烃环丙烷化和烯炔环加成的结构和反应性的实验信息。 建议的研究活动旨在填补这些空白，并开发一个实验接地金π-活化catalyst.The出现的催化剂作为碳碳多键的功能化（π-活化催化）的机制的理解在均相催化在过去十年中最重要的发展之一的阳离子金（I）络合物。 这些转化通常表现出高效率，优异的原子经济性，以及高区域和立体选择性，使它们在靶向合成和药物开发中的应用特别有吸引力。 本项目开展的研究活动将提供机制信息，促进这一重要的合成转化家族的持续发展。 此外，与这一项目有关的研究活动与研究生和本科生研究参与者的科学教育和培训完全结合起来，包括来自传统上在科学领域代表性不足的族裔群体的学生。