Gas-Phase Studies of Organic Reaction Mechanisms: Stereochemistry, Eliminations, and Catalytic Intermediates

有机反应机理的气相研究：立体化学、消除和催化中间体

• 批准号: 0716147
• 负责人: Scott Gronert
• 金额: $ 33万
• 依托单位: Virginia Commonwealth University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2007
• 资助国家: 美国
• 起止时间: 2007-11-15 至 2010-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0716147&HistoricalAwards=false
• 关键词: Gas; Phase; Studies; Organic; Reaction

The research will employ a combination of experimental and computational techniques to study fundamental organic reactions in the gas phase. Although it is well accepted that gas-phase methods can provide important insights into the mechanisms of organic processes, investigations of reaction stereochemistry have been limited because mass spectrometry provides limited 3-dimensional structural information. In this work, Professor Gronert will overcome this problem by using isotopic-labeling strategies to identify the stereochemical preferences of elimination and catalytic cyclopropanation reactions. Both processes play pivotal roles in organic synthesis and have been the subject of numerous studies in solution. In the catalytic reactions, the studies will take advantage of the ability of mass spectrometry to isolate and study model intermediates that are too reactive to be characterized in solution. Two key goals in the work are (1) identifying intrinsic (i.e., solvent-free) reaction preferences and (2) establishing correlations between behavior in the gas-phase and solution. This information is critical for understanding the role that mass spectrometry can play in the development of new reagents and catalysts.With this Research Award, the Organic and Macromolecular Chemistry Program supports the research of Scott Gronert of Virginia Commonwealth University. Professor Gronert is using mass spectrometry to study organic reactions in the gas phase. This approach eliminates complicating interactions with solvent molecules and can reveal the fundamental factors that govern the course of the reaction process. The mass spectrometry data will be compared with those from computational modeling and provide information on the reliability of computational models in catalytic systems. The results from this project can be used in the development of new, cost-efficient methods for rapidly assessing the capabilities of potential catalysts for organic synthesis. Student training and involvement is integrated into the project and the participants will gain valuable experience with modern instrumentation and chemical techniques.

这项研究将采用实验和计算技术相结合的方法来研究气相中的基本有机反应。尽管人们普遍认为气相方法可以为有机过程的机理提供重要的见解，但由于质谱法提供的三维结构信息有限，因此对反应立体化学的研究受到限制。在这项工作中，Gronert教授将通过使用同位素标记策略来确定消除和催化环丙烷反应的立体化学偏好来克服这一问题。这两个过程在有机合成中都起着关键作用，并且一直是溶液中大量研究的主题。在催化反应中，研究将利用质谱法分离和研究在溶液中过于活跃而无法表征的模型中间体的能力。工作中的两个关键目标是(1)确定固有（即无溶剂）反应偏好和(2)建立气相和溶液行为之间的相关性。这些信息对于理解质谱法在新试剂和催化剂的开发中所起的作用至关重要。有了这个研究奖，有机和大分子化学项目支持弗吉尼亚联邦大学的斯科特·格罗内特的研究。格罗内特教授正在使用质谱法研究气相中的有机反应。这种方法消除了与溶剂分子复杂的相互作用，可以揭示控制反应过程的基本因素。质谱数据将与计算模型的数据进行比较，并提供催化系统中计算模型可靠性的信息。这个项目的结果可以用于开发新的、经济有效的方法来快速评估潜在的有机合成催化剂的能力。学生的培训和参与被整合到项目中，参与者将获得现代仪器和化学技术的宝贵经验。