CAREER: Development of catalytic enantioselective hydrofunctionalizations of alkenes

通过这一职业奖，美国国家科学基金会化学部化学合成计划支持加州大学欧文分校化学系谢尔盖·V·普罗宁教授的研究。Pronin教授和他的学生正在开发新的方法，将含有两个碳原子(即烯烃)之间的双键的化合物直接转化为含有氮(胺)、氧氢基(醇)及其衍生物的化合物。反应条件温和，使用环境友好的材料，使新的合成路线在节约能源和关键元素方面具有吸引力。这些新分子是在工业，特别是制药工业中广泛使用的有价值的化学物质。正在研究的化学转化是有机化学领域的一个长期挑战。这项研究正在利用未被探索的化学反应模式，并为这些问题提出新的一般解决方案。普罗宁教授的实验室东道主？在大学的一天？作为UCI物理科学实验室实验和活动(LEAPS)计划的一部分，该计划旨在教育中学生了解他们在物理科学领域存在的机会。与UCI的其他教员合作，研究团队从当地一所少数民族学生人数较少的社区学院-圣地亚哥峡谷学院-招募和接待学生，在夏季为期十周，提供合成有机化学领域的研究经验。该项目预计将提高少数族裔学生对STEM研究和就业机会的认识。这项研究还为下一代化学家提供了丰富的培训基础，为社区大学参与化学研究的学生创造了机会。这项研究正在利用自由基-极性交叉反应，并开发新的对映选择性方法，通过地球上丰富的钴物种进行烯烃的氢化功能化。这些转化将容易的氢原子转移事件与所产生的烷基自由基和相关中间体氧化成相应的碳正离子或其合成的等价物相结合。然后，这些物种可以与亲核试剂反应，生成新的官能团。组合工艺相当于Bronsted酸催化的氢官能化，但在没有酸的情况下进行。这些反应的异常温和的条件适应了广泛的底物范围，并促进了相应的对映选择性反应的发展。总体而言，这项研究提供了直接和一般的途径，从现成的起始材料中获得有价值的可伸缩构件，并产生了关于碳正离子和相关亲电中间体的基本反应性的新知识。这项研究还为下一代化学家提供了丰富的培训基础，为参与化学研究有限的社区大学的学生创造了机会，并提高了中学生对STEM领域未来职业选择的认识。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。

With this CAREER Award, the Chemical Synthesis Program of the NSF Division of Chemistry is supporting the research of Professor Sergey V. Pronin of the Department of Chemistry at the University of California Irvine. Professor Pronin and his students are developing new methods for the direct conversion of compounds that contain a double bond between two carbon atoms (i.e., alkenes) to compounds that contain nitrogen (amines), a oxygen-hydrogen groups (alcohols), and their derivatives. The reaction conditions are mild and use environmentally-abundant materials, making the new synthetic routes attractive for conserving both energy and critical elements. These new molecules are valuable chemicals used extensively in industry, especially the pharmaceutical industry. The chemical transformations being studied are a long-standing challenge in the field of organic chemistry. This research is taking advantage of underexplored patterns of chemical reactivity and producing new and general solutions to these problems. Professor Pronin's laboratory host ?Day at College? events as a part of the Laboratory Experiments and Activities in the Physical Sciences (LEAPS) program at UCI, which is aimed at educating middle school students about the opportunities that exist for them in the physical sciences. In collaboration with other faculty at UCI, the research team recruit and host students from a local community college with a large population of underrepresented minority students, Santiago Canyon College, for ten weeks during the summer to provide research experiences in the field of synthetic organic chemistry. This program is expected to increase awareness of minority students for STEM research and job opportunities. The research is also providing a rich training ground for the next generation of chemists, generating opportunities for students from community colleges with limited engagement in chemistry research.This research is leveraging radical-polar crossover reactivity and developing new enantioselective methods for the hydrofunctionalization of alkenes via earth-abundant cobalt species. These transformations combine facile hydrogen atom transfer events with oxidation of the resulting alkyl radicals and related intermediates to the corresponding carbocations or their synthetic equivalents. These species can then undergo reactions with nucleophiles to generate new functional groups. The combined process serves as an equivalent of Bronsted acid-catalyzed hydrofunctionalizations but proceeds in the absence of an acid. The exceptionally mild conditions of these reactions accommodate a broad substrate scope and facilitate development of the corresponding enantioselective reactions. Overall, this research is providing direct and general access to valuable scalemic building blocks from readily available starting materials and producing new knowledge of the fundamental reactivity of carbocations and related electrophilic intermediates. The research is also providing a rich training ground for the next generation of chemists, generating opportunities for students from community colleges with limited engagement in chemistry research, and increasing awareness of middle school students to future career options in STEM fields.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.