A Dehydro-Diels-Alder Reaction

通过该奖项，化学合成项目将支持匹兹堡大学的Kay M. Brummond教授开发分子内二脱氢- diels - alder （IMDDA）反应，以制备萘衍生物和苯合杂环。这些物质是各种应用的宝贵组成部分，但不易通过已知的合成方法获得。IMDDA的操作简单性和可扩展性有可能促进以前难以获得的芳香族化合物的制备，并有可能应用于有机发光二极管，液晶，显像剂，手性配体和药物。将探索可持续和绿色的苯乙烯基化合物作为IMDDA前体的制备方法。热脱除IMDDA加合物中的氢气以形成芳香族化合物，为试剂氧化方案提供了一种环境友好的替代方案。这项研究将为研究生提供最先进的合成有机化学方面的培训，该项目具有重大的潜在科学影响。在IMDDA中，系连苯乙烯基和炔基的[2+4]环加成之后是分子氢的热损失，从而得到萘衍生物。本研究有望显著扩大IMDDA的范围和应用，使该反应成为制备功能化萘、二氢萘和苯并杂环化合物的可行途径。此外，将开发IMDDA反应条件来控制反应途径的发散，以选择性和可预测地生成芳香族或二氢芳香族产物。通过机理研究，可以更好地理解无受体脱氢反应，并应用计算洞察力来指导反应条件、底物和靶标的选择。最后，期望这些热反应条件能与多种官能团相容，从而适于制备高取代和多种官能团化的萘和其他有价值的芳香族化合物。

With this award, the Chemical Synthesis program is supporting Professor Kay M. Brummond at the University of Pittsburgh to develop the intramolecular didehydrogenative-Diels-Alder (IMDDA) reaction to prepare naphthalene derivatives and benzo-fused heterocycles. These substances are valuable building blocks for a variety of applications but are not readily available through known synthetic methods. The operational simplicity and scalability of the IMDDA has the potential to facilitate preparation of previously inaccessible aromatic compounds with the potential for application to organic light emitting diodes, liquid crystals, imaging agents, chiral ligands, and pharmaceuticals. Sustainable and green alternatives for the preparation of styrenyl compounds as IMDDA precursors will be explored. The thermal removal of hydrogen gas from IMDDA adducts to form aromatic compounds offers an environmentally benign alternative to reagent-based oxidation protocols. This research will provide state of the art training in synthetic organic chemistry for graduate students on a project with significant potential scientific broader impacts. In the IMDDA, [2+4] cycloaddition of tethered styrenyl and alkynyl groups is followed by thermal loss of molecular hydrogen to provide a naphthalene derivative. This research is expected to significantly expand the scope and utility of the IMDDA, making this reaction a viable avenue for the preparation of functionalized naphthalenes, dihydronaphthalenes and benzofused heterocycles. In addition, IMDDA reaction conditions will be developed to control the diverging reaction pathways for the selective and predictable formation of either an aromatic or a dihydroaromatic product. Through mechanistic studies, a better understanding of the acceptorless dehydrogenation reaction will be developed, and computational insight will be applied to guide the selection of reaction conditions, substrates and targets. Finally, it is expected that these thermal reaction conditions will be compatible with a variety of functionality, and thus amenable to the preparation of highly substituted and diversely functionalized naphthalenes and other valuable aromatic compounds.