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.

在化学部化学催化计划资助的该项目中，希望学院化学系的杰弗里·约翰逊（Jeffrey B. Johnson）教授正在开发新方法，通过激活碳碳键来有效地生产有机化合物。碳碳键非常普遍，构成了来自生物以及许多聚合物和其他重要材料的分子框架。尽管率高，但很少有反应条件可以选择性地打破这些键。约翰逊教授及其本科合作者小组正在努力理解这些少数已知反应的过程。 他们正在使用这些信息来开发新方法来激活和转化碳碳键。这些目标的成功实现有望为复杂分子提供更有效的合成途径，包括可以作为潜在药物的生物活性检查的新化合物。本科生通过参与该项目来加强他们的个人科学准备。 反过来，这些本科生是向上界的导师，协助高中生的学生为STEM领域的大学和潜在的未来做准备。 杰弗里·约翰逊（Jeffrey B. Johnson）教授正在开发新的反应，以用于过渡金属催化的激活和碳碳单键的功能化。本科合作者正在对2-吡啶基苄烯酮的铑催化脱轴偶治化进行机械研究，确定能量屏障和鉴定反应中间体。由于刘易斯基本指导组通常是选择性碳 - 碳键激活所必需的，因此努力集中在使用容易删除或操纵的指导组来识别允许使用广泛酮和羧酸衍生物的条件。这些底物的激活，然后与随时可用的PI系统或有机金属结合，有望快速访问具有潜在生物学活动的广泛的复杂分子。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子和更广泛影响的评估来通过评估来获得支持的。

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.