RUI: Carbon-carbon single bond activation as a route to new organic transformations

RUI：碳-碳单键活化作为新有机转化的途径

• 批准号: 1764118
• 负责人: Jeffrey Johnson
• 金额: $ 27.39万
• 依托单位: Hope College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-09-01 至 2022-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1764118&HistoricalAwards=false
• 关键词: RUI; Carbon; carbon; single; bond

In this project funded by the Chemical Catalysis Program of the Chemistry Division, Professor Jeffrey B. Johnson of the Department of Chemistry at Hope College is developing new methods for the efficient production of organic compounds through the activation of carbon-carbon bonds. Carbon-carbon bonds are extremely common, making up the framework of molecules derived from living things as well as many polymers and other important materials. Despite their prevalence, there are few reaction conditions known that can selectively break these bonds. Professor Johnson and his group of undergraduate collaborators are working to understand the processes by which these few known reactions occur. They are using this information to develop new methods to activate and transform carbon-carbon bonds. Successful realization of these goals promises more efficient synthetic routes to complex molecules, including new compounds that can be examined for biological activity as potential pharmaceutical agents. Undergraduate students strengthen their personal scientific preparation through participation in this project. In turn, these undergraduates serve as Upward Bound mentors, assisting at-risk high school students prepare for college and potential futures in STEM fields. Professor Jeffrey B. Johnson is developing new reactions for the transition metal-catalyzed activation and functionalization of carbon-carbon single bonds. Undergraduate collaborators are carrying out the mechanistic investigation of the rhodium-catalyzed decarbonylation of 2-pyridylbenzophenones, determining energy barriers and identifying reaction intermediates. As Lewis basic directing groups are generally required for selective carbon-carbon bond activation, efforts focus on the use of readily removed or manipulated directing groups for the identification of conditions that allow the use of a broad range of ketones and carboxylic acid derivatives. The activation of these substrates, followed by coupling with readily available pi systems or organometallics, promises rapid access to a wide range of complex molecules with potential biological activity.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在这个由化学系化学催化计划资助的项目中，霍普学院化学系的杰弗里·B·约翰逊教授正在开发通过激活碳-碳键高效生产有机化合物的新方法。碳-碳键是非常常见的，它构成了来自生物的分子以及许多聚合物和其他重要材料的框架。尽管它们普遍存在，但几乎没有已知的反应条件可以选择性地打破这些键。约翰逊教授和他的本科生合作者团队正在努力了解这些鲜为人知的反应发生的过程。他们正在利用这些信息开发新的方法来激活和转化碳-碳键。这些目标的成功实现保证了获得复杂分子的更有效的合成路线，包括可以作为潜在药剂检查生物活性的新化合物。本科生通过参与该项目加强个人的科学准备。反过来，这些本科生充当向上的导师，帮助高危高中生为大学和STEM领域的潜在未来做准备。杰弗里·B·约翰逊教授正在为过渡金属催化的碳-碳单键的活化和功能化开发新的反应。本科生的合作者正在开展2-吡啶基二苯甲酮在铑催化下的脱羰反应的机理研究，确定能垒并确定反应中间体。由于选择性碳-碳键活化通常需要Lewis碱性导向基团，因此努力集中于使用容易移除或操纵的导向基团，以确定允许使用广泛范围的酮和羧酸衍生物的条件。激活这些底物，然后与现成的PI系统或有机金属相结合，有望快速获得具有潜在生物活性的广泛复杂分子。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Pyridine-directed carbon–carbon single bond activation: Rhodium-catalyzed decarbonylation of aryl and heteroaromatic ketones

吡啶引导的碳-碳单键活化：铑催化芳基和杂芳酮的脱羰

• DOI: 10.1016/j.tetlet.2021.153132
• 发表时间: 2021
• 期刊: Tetrahedron Letters
• 影响因子: 1.8
• 作者: Wagner, Cole J.;Salisbury, Eric A.;Schoonover, Erik J.;VanderRoest, Jacob P.;Johnson, Jeffrey B.
• 通讯作者: Johnson, Jeffrey B.