Heterocycle Synthesis Through Reversible Allylic Alcohol Transposition and Stereoselective Capture

在这个由化学部合成计划资助的项目中，匹兹堡大学的Paul Floreancig教授开发了新的化学反应，其中可逆性与第二步相结合，以增加分子复杂性并产生立体中心。 该方法是将含有亲电子基团的烯丙基醇暴露于氧化物或其他影响非立体选择性转座的催化剂。转座将继续进行，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。 一些元素将被纳入到反应基板，以证明反应结果可以通过应用程序的基本原理和分子建模合理地操纵。目标结构的选择是由于它们与天然产物合成的相关性。将在这项工作中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努力。这将有利于药物化学和材料科学领域。 用于这些反应的温和条件将使该过程对化学制造应用具有吸引力。 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，突出的方式，热力学和动力学可以被操纵复杂的反应设计，并在使用的旅行资金，目前在大学的研讨会，有一个高入学率的少数民族学生。 此外，该项目还为研究生提供研究培训，并为劳动力发展做出贡献。

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.