Cobalt-Catalyzed Cycloadditions and Hydrofunctionalizations of Alkenes

有了这个奖项，NSF化学部的化学催化计划支持了俄亥俄州州立大学的Thaliyil RajanBabu教授的研究。RajanBabu教授正在开发高效和选择性的反应，可以为医药，农业或材料应用的有机分子合成提供实用的方法。 在这种情况下，正在研究涉及使用大量可用和可持续的原料起始材料的新反应，如乙烯，丁二烯，异戊二烯，丙烯酸甲酯，地球上丰富的金属，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，即稳定分子的活化及其随后选择性地掺入其他分子。它还为化学的基础发现提供了极好的机会。 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，并采用了分析，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小组参与了与哥伦布公立学校、俄亥俄州科学奥林匹克竞赛和俄勒冈州立大学REEL（增强学习的研究经验）项目的外联活动。后者是通过结合最先进的仪器，并提供使用这种仪器来解决具有挑战性的化学问题的经验，改造本科实验室的经验。 RajanBabu教授的其他推广活动包括在大学，包括主要是本科院校，工业研究中心和会议上讲课。1，3-二烯和烯炔是一类容易获得的底物，很少用作分子间不对称C-C和C-G（G =主族元素）键形成反应的前体。 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异二聚的例子。 反应机理的研究指出，一种新的高活性的低价阳离子钴（I）物种作为该反应的可能催化剂。 初步结果表明，还有其他反应可以被类似的物种催化。 RajanBabu小组正在开发这些反应，包括不对称硼氢化、硅氢化和氢化酰化。 拟议的研究为更有效和选择性地合成生物相关靶标及其同源物提供了强大的工具，并为我们的环境友好过程库增添了新的内容。 在基本水平上，这些反应的范围和局限性及其机理研究揭示了实现重要有机反应的化学，区域和立体选择性的新方法。俄勒冈州立大学的REEL项目正在向本科生实验室引入一种先进的动力学实验，该实验使用原位红外光谱法。 这些实验都是经过精心挑选的，这样小班的所有学生都可以从正在进行的反应中单独收集几分钟的数据（例如，硼氢化物还原酮），然后在提交完整的报告进行评估之前进行动力学分析。 该奖项旨在向学生介绍动力学和光谱学，尽管这两个主题是物理化学和有机化学的支柱，但目前我们的学生很少在常规实验室课程中获得实践培训。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。

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.