Asymmetric Hydrovinylation of 1,3-Dienes

在这个由化学学部化学催化项目支持的项目中，RajanBabu教授的目标是利用现成的起始材料（如乙烯和简单的1,3-二烯）开发高效和选择性的新反应，以生产有价值的化学中间体。这些中间体可用于医药、农业和聚合物产品的合成。通过一种依赖于新催化剂的制备和对反应的详细研究的方法，PI的小组解决了两个重大挑战：激活稳定分子以提高其反应活性和反应的高选择性。寻找这些具有挑战性问题的解决方案可以为在催化领域产生影响的基础发现提供机会。本研究的跨学科性质，涵盖了有机、无机和有机金属化学领域，并采用了分析化学、物理有机化学和计算化学的技术，为培养各个层次的学生提供了一个有价值的平台。1,3-二烯，如丁二烯和异戊二烯，是很容易获得的原料，很少用于精细化学品的合成。简单烷基或芳基取代二烯的低反应活性及其构象迁移率是该区域活性缺乏的主要原因。PI的小组最近开发了第一个高对映选择性钴催化乙烯加成到各种1,3-二烯的例子。这些创新方法的扩展提供了高活性的新中间体，可用于加工成与医学相关的化合物。拟议的研究扩大了起始材料的范围，通过减少制备复杂分子所需的合成步骤，进一步增强了该方法在有机合成中的能力。由于乙烯可以从生物乙醇中提取，这些方法增加了可持续过程的曲目。项目负责人负责将一个研究模块引入大二学生的实验室。本模块中的实验经过精心挑选，使大班学生熟悉有机化学的一些与选择性和可持续性有关的现代方面。

In this project supported by the Chemical Catalysis program of the Chemistry Division, Professor RajanBabu aims to develop efficient and selective new reactions of readily available starting materials such as ethylene and simple 1,3-dienes for the production of valuable chemical intermediates. These intermediates could be used for the synthesis of pharmaceutical, agricultural and polymer products. Through an approach that relies on the preparation of new catalysts, and detailed study of reactions, the PI's group addresses two significant challenges: activation of stable molecules to enhance their reactivity and high selectivity in their reactions. Search for solutions to such challenging problems can provide opportunities to make fundamental discoveries having an impact in the field of catalysis. 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, provides a valuable platform for training students at every level.1,3-Dienes such as butadiene and isoprene are readily accessible starting materials that have been used only rarely for the synthesis of fine chemicals. Low reactivity of simple alkyl or aryl substituted dienes and their conformational mobility are largely responsible for this dearth of activity in this area. The PI's group recently developed the first examples of highly enantioselective cobalt-catalyzed additions of ethylene to a wide variety of 1,3-dienes. Extensions of these innovative methods provide highly reactive new intermediates that are useful for elaboration into medicinally relevant compounds. Proposed research to expand the scope of starting materials further enhances the power of this method in organic synthesis by decreasing the synthetic steps required to prepare complex molecules. Since ethylene can be derived from bio-ethanol, these methods add to the repertoire of sustainable processes. The PI is involved in the introduction of a research module to a sophomore laboratory. The experiments in this module are carefully chosen to familiarize a large class with some modern aspects of organic chemistry that relate to selectivity and sustainability.