Asymmetric Hydrovinylation of 1,3-Dienes

在化学系化学催化计划的支持下，RajanBabu教授致力于开发高效和选择性的新反应，利用容易获得的原料，如乙烯和简单的1，3-二烯来生产有价值的化学中间体。这些中间体可用于合成医药、农业和聚合物产品。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的团队解决了两个重大挑战：激活稳定的分子以提高其反应活性和反应中的高选择性。寻找这些具有挑战性的问题的解决方案可以提供机会，使基础性发现对催化领域产生影响。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，为各级学生的培训提供了一个宝贵的平台。丁二烯和异戊二烯等1，3-二烯是很容易获得的起始原料，很少用于合成精细化学品。简单的烷基或芳基取代二烯的低反应性和它们的构象迁移性是这一领域活性缺乏的主要原因。PI的小组最近开发了第一批高对映选择性钴催化的乙烯与多种1，3-二烯的加成反应的例子。这些创新方法的延伸提供了高活性的新中间体，这些中间体有助于精制成医学上相关的化合物。拟议的研究扩大了原料的范围，通过减少制备复杂分子所需的合成步骤，进一步增强了这种方法在有机合成中的威力。由于乙烯可以从生物乙醇中提取，这些方法增加了可持续工艺的保留量。PI参与了将研究模块引入二年级实验室的工作。本单元中的实验是精心挑选的，目的是让大班学生熟悉与选择性和可持续性有关的有机化学的一些现代方面。

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.