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.

在由化学部综合计划资助的该项目中，匹兹堡大学的Paul Floreancig教授开发了新的化学反应，其中可逆性与提高分子复杂性并产生立体中心的次要步骤相结合。 该方法是暴露于含有亲电的氧化物或氧化rhen的其他催化剂的烯丙基醇。换位将进行，直到发生分子内反应发生，在该反应中，立体化学控制将由热力学，动力学或催化剂控制决定。 将在反应底物中纳入许多元素，以证明可以通过基本原理和分子建模的应用来合理地操纵反应结果。由于与天然产物的合成相关，因此选择了目标结构。在这项工作中将开发的立体控制与环形成的偶联可以显着减少复杂分子合成所需的努力。这将使药物化学和材料科学领域受益。 这些反应的轻度条件将使该过程对化学制造应用有吸引力。 这项工作的更广泛的影响在于使用这些过程作为一种工具，以突出可以操纵热力学和动力学的方式来进行复杂的反应设计，并使用旅行资金在学院举行研讨会，而学院的研讨会很高，而这些研讨会的人数众多。 此外，该项目为研究生提供了研究培训，并为劳动力发展做出了贡献。