Methods for Regiocontrol in Polarized Polyene Systems

偏振多烯系统中的区域控制方法

• 批准号: 2154880
• 负责人: Justin Mohr
• 金额: $ 50.4万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154880&HistoricalAwards=false
• 关键词: Methods; Regiocontrol; Polarized; Polyene; Systems

With the support of the Chemical Synthesis program in the Division of Chemistry, Justin Mohr of the University of Illinois at Chicago (UIC) is studying new techniques to control the nature of chemical transformations occurring from a class of versatile and readily generated intermediates called 'polarized polyenes.' The type of reactivity being explored complements established methods for organic synthesis and it is anticipated to streamline the manufacture of pharmaceutical agents, agrochemicals, and other useful advanced materials. In conjunction with catalyst discovery efforts, this research will target new strategies to precisely control the atomic connectivity and three-dimensional structure of complex products obtained from polarized polyenes. Crucially, and because these starting materials are capable of reacting in a variety of different ways, the research promises important fundamental advances in the area of divergent chemical pathways management. A demographically diverse group of undergraduate and graduate students within the Mohr laboratory will conduct the funded research. These individuals will gain valuable technical and scientific skills of relevance to potential future careers in the science, technology, engineering, and mathematics (STEM)-based workforce. The broader impacts of the project will include outreach activities conducted by the Mohr research team as they engage with Chicago-area K-12 students to promote science education. In addition, and to complement these and other ongoing efforts to broaden participation, Dr. Mohr actively recruits undergraduate students belonging to underrepresented groups to become involved in chemical research in his laboratory at UIC, a minority-serving institution (MSI).The development of efficient strategies for the assembly of polyfunctional molecules is facilitated by gaining new insights into the fundamental reactivity of progressively more complex intermediates. It is from this standpoint that the funded project focuses on the development of a suite of gamma-selective transformations from conjugated dienol systems [e.g., 1-(tert-butyldimethylsilyloxy)-1,3-cyclohexadiene], each example of which may provide a useful new synthetic tool for the elaboration of desirable target classes. Specific aims of the research include: (1) development of copper- and nickel-catalyzed stereoselective C–C bond forming reactions through examination of novel chiral ligand and chiral auxiliary designs, (2) expansion of metal-catalyzed coupling techniques to include problematic primary halide coupling partners, (3) examination of single-electron oxidation of dienol ethers to generate novel radical cation intermediates exhibiting regioselective reactivity, and (4) exploration of transition metal-catalyzed, site-selective C–heteroatom bond formation in polyene systems. Ultimately, the research is expected to help build a growing understanding of the basic factors that influence and control regio- and stereo-selectivity in polyene systems.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.

在化学系化学合成项目的支持下，伊利诺伊大学芝加哥分校 (UIC) 的贾斯汀·莫尔 (Justin Mohr) 正在研究新技术，以控制一类多功能且易于生成的中间体（称为“极化多烯”）发生的化学转化的性质。正在探索的反应类型补充了现有的有机合成方法，预计将简化药剂、农用化学品和其他有用先进材料的制造。结合催化剂发现工作，这项研究将瞄准新策略，以精确控制从极化多烯获得的复杂产物的原子连通性和三维结构。至关重要的是，由于这些起始材料能够以各种不同的方式发生反应，因此该研究有望在不同化学途径管理领域取得重要的基础性进展。莫尔实验室内由不同人口组成的本科生和研究生群体将开展这项资助的研究。这些人将获得与科学、技术、工程和数学 (STEM) 劳动力未来潜在职业相关的宝贵技术和科学技能。该项目更广泛的影响将包括莫尔研究团队在与芝加哥地区 K-12 学生合作以促进科学教育时开展的外展活动。此外，为了补充这些和其他持续扩大参与的努力，Mohr 博士积极招募属于代表性不足群体的本科生，参与他在 UIC（一家少数族裔服务机构 (MSI)）的实验室的化学研究。通过对日益复杂的基本反应性获得新的见解，促进了多官能分子组装的有效策略的开发。 中间体。正是从这个角度来看，该资助项目的重点是从共轭二烯醇系统[例如1-(叔丁基二甲基硅氧基)-1,3-环己二烯]开发一套γ选择性转化，其中每个例子都可以为阐述所需目标类别提供有用的新合成工具。该研究的具体目标包括：（1）通过检查新型手性配体和手性辅助设计来开发铜和镍催化的立体选择性C-C键形成反应，（2）扩展金属催化偶联技术以包括有问题的初级卤化物偶联伙伴，（3）检查二烯醇醚的单电子氧化以产生新型自由基阳离子 表现出区域选择性反应活性的中间体，以及（4）探索多烯体系中过渡金属催化的、位点选择性的C-杂原子键形成。最终，这项研究预计将有助于加深对影响和控制多烯系统区域选择性和立体选择性的基本因素的了解。该奖项反映了 NSF 的法定使命，并通过使用基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。