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.

通过该奖项，化学系的化学催化计划是在杜克大学化学系教授的资助罗斯·维登霍弗教授的基础研究，用于基于黄金元素的催化反应研究，这使简单的有机分子有效地转化为更复杂的分子。 有效，有选择地将有机化合物转化为更高价值的产品的新催化方法具有转化各种化学生产的潜力。 在该项目中，正在仔细研究其在化学转化中的最佳应用中涉及的特定反应步骤的机制。拟议的研究活动正在整合到研究生和本科生研究人员的科学教育和培训中，其中包括传统上在科学中人数不足的团体的学生。研究生正在参加通过杜克大学研究生院提供的教育活动。 研究生和本科生还正在进行社区外展活动，并正在开发与催化和协调化学有关的演示。ProfessorWidenhoefer正在研究黄金（I）Pi-Accipation催化的机制，包括碳碳多键的加水功能以及Enynes andernes and Cyclation and anynes and Crosectrates and Isdrates and Isdrates and Cycrates and castrates。 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. 正在追求研究活动以填补这些空白，并对金PI-Activation催化的机制有了实验基础的理解。 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稳定和（4）在金催化的Enyne Cycloadtition中形成的bicyclo- [3.2.0] - heptenes的银催化水屈服和骨骼重排的机制。 预计该提案中概述的活动的实现将以有意义的方式理解金（I）催化的水功能化的机理以及金碳纤维复合物的结构和反应性。