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Cobalt-Catalyzed Cycloadditions and Hydrofunctionalizations of Alkenes

钴催化的烯烃环加成和氢官能化

基本信息

批准号：
1900141
负责人：
Thaliyil RajanBabu
金额：
$ 48.5万
依托单位：
Ohio State University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-08-01 至 2023-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900141&HistoricalAwards=false
关键词：
Cobalt Catalyzed Cycloadditions Hydrofunctionalizations Alkenes

项目摘要

With this award, the Chemical Catalysis Program of the NSF Division of Chemistry is supporting the research of Professor Thaliyil RajanBabu of The Ohio State University. Professor RajanBabu is developing efficient and selective reactions that can offer practical approaches to the synthesis of organic molecules for medicinal, agricultural, or material applications. In this context, new reactions involving the use of abundantly available and sustainable feedstock starting materials such as ethylene, butadiene, isoprene, methyl acrylate, earth-abundant metals such as cobalt and nickel, and ligands that bind to those metals are being examined. This research is solving two significant challenges in this area, namely, activation of stable molecules and their subsequent selective incorporation into other molecules. It is also providing outstanding opportunities for fundamental discoveries in chemistry. The interdisciplinary nature of this research, which covers the areas of organic, inorganic and organometallic chemistry, and employs the techniques from analytical, physical organic, and computational chemistry, also provides a useful platform for training undergraduate and graduate students. The RajanBabu group is involved in outreach activities with Columbus public schools, the Ohio Science Olympiad, and the REEL (Research Experiences to Enhance Learning) program at OSU. The later is transforming the undergraduate laboratory experience by incorporating state of the art instrumentation and providing experience on the use of this instrumentation to solve challenging chemical problems. Other outreach activities of Professor RajanBabu include giving lectures at universities including predominantly undergraduate institutions, industrial research centers, and conferences.1,3-Dienes and enynes are classes of readily accessible substrates that have been used only rarely as precursors in intermolecular asymmetric C-C and C-G (G = a main group element) bond-forming reactions. The RajanBabu group recently reported the first examples of highly enantioselective cobalt(I)-catalyzed heterodimerization of a diene and an acrylate. A study of the reaction mechanism points to a new highly reactive low-valent cationic cobalt (I) species as a possible catalyst for this reaction. Preliminary results suggest that there are other reactions that could be catalyzed by a similar species. The RajanBabu group is developing these reactions, including asymmetric hydroboration, hydrosilylation, and hydroacylation. The proposed research is providing powerful tools for more efficient and selective synthesis of biologically relevant targets and their congeners, and adding to our repertoire of environmentally benign processes. At a fundamental level, the scope and limitations of these reactions and their mechanistic studies are revealing new ways of achieving chemo-, regio- and stereoselectivities of important organic reactions. The REEL program at OSU is introducing an advanced kinetic experiment using in situ IR spectroscopy to the undergraduate laboratory. The experiments are carefully chosen so that all students from a small class can collect data individually for a few minutes from an on-going reaction (borohydride reduction of a ketone, for example), and, do the kinetic analysis later, before submitting a full report for evaluation. This is introducing them to kinetics and spectroscopy, two topics in which few of our students currently get practical training in their regular laboratory classes, even though these topics are mainstays in both physical and organic chemistry.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.

通过这一奖项，美国国家科学基金会化学部的化学催化计划正在支持俄亥俄州立大学的Thaliyil RajanBabu教授的研究。RajanBabu教授正在开发高效和选择性的反应，可以为合成用于医药、农业或材料应用的有机分子提供实用的方法。在这方面，正在审查涉及使用大量可获得和可持续的原料原料的新反应，如乙烯、丁二烯、异戊二烯、丙烯酸甲酯、富含地球的金属，如钴和镍，以及与这些金属结合的配体。这项研究正在解决这一领域的两个重大挑战，即稳定分子的激活和随后它们选择性地结合到其他分子中。它还为化学领域的基础发现提供了绝佳的机会。这项研究的跨学科性质，涵盖了有机、无机和有机金属化学领域，并使用了分析、物理有机和计算化学的技术，也为培养本科生和研究生提供了一个有用的平台。RajanBabu小组参与了哥伦布公立学校、俄亥俄州科学奥林匹克竞赛和俄亥俄州立大学的REEL(增强学习的研究经验)计划的外联活动。后者正在通过整合最先进的仪器和提供使用这种仪器来解决具有挑战性的化学问题的经验来改变本科生的实验室经验。RajanBabu教授的其他推广活动包括在大学讲课，包括主要是本科生机构、工业研究中心和会议。1，3-二烯和烯炔是一类容易获得的底物，很少被用作分子间不对称C-C和C-G(G=主要基团元素)成键反应的前体。RajanBabu小组最近报道了第一个高对映选择性钴(I)催化的二烯和丙烯酸酯的异二聚化的例子。对反应机理的研究表明，一种新的高活性低价阳离子钴(I)物种可能是该反应的催化剂。初步结果表明，还有其他反应可以由类似的物种催化。RajanBabu小组正在发展这些反应，包括不对称氢硼化、氢硅化和氢酰化。这项拟议的研究为更有效和更有选择性地合成与生物相关的靶标及其同系物提供了强大的工具，并增加了我们的环境友好过程。在基本水平上，这些反应的范围和局限性及其机理研究正在揭示实现重要有机反应的化学、区域和立体选择性的新方法。俄亥俄州立大学的REEL项目正在将一项使用原位红外光谱的先进动力学实验引入本科生实验室。这些实验经过精心挑选，以便小班的所有学生都可以单独收集正在进行的反应(例如，酮的硼氢化物还原)的几分钟数据，并在稍后进行动力学分析，然后提交完整的报告进行评估。这是向他们介绍动力学和光谱学，这两个主题目前我们的学生很少在他们的常规实验室课程中得到实践培训，尽管这些主题是物理化学和有机化学的主干。这个奖项反映了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。