Heterocycle Synthesis Through Reversible Allylic Alcohol Transposition and Stereoselective Capture

通过可逆烯丙醇转座和立体选择性捕获合成杂环

• 批准号: 1151979
• 负责人: Paul Floreancig
• 金额: $ 39万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-09-01 至 2015-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1151979&HistoricalAwards=false
• 关键词: Heterocycle; Synthesis; Through; Reversible; Allylic

In this project funded by the Synthesis Program of the Chemistry Division, Prof. Paul Floreancig at the University of Pittsburgh develops new chemical reactions in which reversibility is coupled with a secondary step to increase molecular complexity and generate stereocenters. The approach is to expose allylic alcohols that contain an electrophilic group to rhenium oxide or other catalysts that effect non-stereoselective transpositions. The transposition will proceed until an intramolecular reaction occurs in which stereochemical control will be dictated by thermodynamic, kinetic, or catalyst control. A number of elements will be incorporated into the reaction substrates to demonstrate that reaction outcomes can be manipulated rationally through applications of basic principles and molecular modeling. The target structures have been selected due to their relevance to the synthesis of natural products. The coupling of stereocontrol with ring formation that will be developed in this work can significantly reduce the effort that is required for complex molecule synthesis. This will benefit the fields of medicinal chemistry and materials science. The mild conditions that are used for these reactions will make the processes attractive for chemical manufacturing applications. The broader impacts of this work lie in the use of these processes as a tool for highlighting the manner in which thermodynamics and kinetics can be manipulated for complex reaction design, and in the use of travel funds to present seminars at colleges that have a high enrollment of underrepresented minority students. In addition, this project provides research training to graduate students and contributes to workforce development.

在这个由化学部合成项目资助的项目中，匹兹堡大学的 Paul Floreancig 教授开发了新的化学反应，其中可逆性与二级步骤相结合，以增加分子复杂性并生成立体中心。 该方法是将含有亲电基团的烯丙醇暴露于氧化铼或其他可实现非立体选择性转位的催化剂。转座将持续进行，直到发生分子内反应，其中立体化学控制将由热力学、动力学或催化剂控制决定。 许多元素将被纳入反应底物中，以证明可以通过应用基本原理和分子建模来合理地操纵反应结果。选择目标结构是因为它们与天然产物的合成相关。这项工作中将开发的立体控制与环形成的耦合可以显着减少复杂分子合成所需的工作。这将有利于药物化学和材料科学领域。 这些反应所使用的温和条件将使这些过程对化学制造应用具有吸引力。 这项工作更广泛的影响在于使用这些过程作为工具来强调如何操纵热力学和动力学来进行复杂的反应设计，以及使用差旅费在少数族裔学生入学率较高的大学举办研讨会。 此外，该项目还为研究生提供研究培训，并有助于劳动力发展。