Mechanistic studies relevant to gold pi-activation catalysis

金π活化催化相关机理研究

• 批准号: 1465209
• 负责人: Ross Widenhoefer
• 金额: $ 42万
• 依托单位: Duke University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-09-01 至 2018-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1465209&HistoricalAwards=false
• 关键词: Mechanistic; studies; relevant; gold; pi

With this award, the Chemical Catalysis Program of the Division of Chemistry is funding Professor Ross Widenhoefer in the Department of Chemistry at Duke University for fundamental studies of catalytic reactions based upon the element, gold, that enable the efficient transformation of simple organic molecules into more complex ones. New catalytic methods that efficiently and selectively transform organic compounds into higher value products have the potential to transform various classes of chemical production. Within this project, the mechanisms of specific reaction steps involved in gold-catalyzed reactions are being carefully investigated for their optimal application in chemical transformations. The proposed research activities are being integrated into the scientific education and training of the graduate and undergraduate student researchers, including students from groups traditionally underrepresented in the sciences. Graduate students are participating in educational activities offered through the Duke University Graduate School. Graduate students and undergraduate students are also performing community outreach activities and developing demonstrations related to catalysis and coordination chemistry.Professor Widenhoefer is investigating the mechanisms of gold(I) pi-activation catalysis, including the hydrofunctionalization of carbon-carbon multiple bonds and the cycloaddition of enynes and related substrates. Despite a growing body of work in this area, limited experimental information is available regarding the mechanisms of the gold(I)-catalyzed hydrofunctionalization of carbon-carbon multiple bonds and, likewise, little direct experimental information is available regarding the structure and reactivity of cationic gold carbene complexes and cationic intermediates germane to gold-catalyzed enyne cycloaddition. Research activities are being pursued to fill these gaps and to develop an experimentally-grounded understanding of the mechanisms of gold pi-activation catalysis. The research is addressing four areas of inquiry: (1) the mechanisms of gold-catalyzed intermolecular hydrofunctionalization of carbon-carbon double bonds with strong and weak donor nucleophiles, (2) the extent of gold-carbon electron donation and d-to-pi backbonding in gold carbene complexes, (3) the structure and reactivity of cationic gold cyclopropyl carbene complexes lacking heteroatom stabilization, and (4) the mechanisms of silver-catalyzed hydroarylation and skeletal rearrangement of bicyclo-[3.2.0]-heptenes formed in gold-catalyzed enyne cycloaddition. Realization of the activities outlined in this proposal is expected to contribute in a meaningful way to the understanding of the mechanisms of gold(I)-catalyzed hydrofunctionalization and the structure and reactivity of gold carbene complexes.

凭借这一奖项，化学学部的化学催化项目资助了杜克大学化学系的Ross Widenhoefer教授，以金元素为基础进行催化反应的基础研究，使简单的有机分子能够有效地转化为更复杂的有机分子。有效和选择性地将有机化合物转化为高价值产品的新催化方法有可能改变各种类型的化学生产。在这个项目中，正在仔细研究金催化反应中特定反应步骤的机制，以使其在化学转化中的最佳应用。拟议的研究活动正在纳入研究生和本科生研究人员的科学教育和培训，包括来自传统上在科学领域代表性不足的群体的学生。研究生们正在参加杜克大学研究生院提供的教育活动。研究生和本科生也在进行社区外展活动，并开展与催化和配位化学相关的示范。Widenhoefer教授正在研究金(I) pi活化催化的机制，包括碳-碳多键的加氢化以及烯和相关底物的环加成。尽管在这一领域的工作越来越多，但关于金(I)催化的碳-碳多键加氢功能化机制的实验信息有限，同样，关于与金催化的环加成相关的阳离子金碳烯配合物和阳离子中间体的结构和反应性的直接实验信息也很少。目前正在进行研究活动，以填补这些空白，并发展对金活化催化机制的实验基础理解。该研究涉及四个调查领域：(1)研究了金催化的碳碳双键与强弱亲核试剂的分子间加氢功能化机理；(2)金碳配合物中金-碳电子给体和d-to-pi回键的程度；(3)缺乏杂原子稳定的阳离子金环丙基碳配合物的结构和反应性。(4)银催化双[3.2.0]-庚烯在金催化环加成中形成的氢化芳基化和骨架重排机理。本提案中概述的活性的实现有望对理解金(I)-催化的加氢功能化机制以及金碳配合物的结构和反应性做出有意义的贡献。