A Dehydro-Diels-Alder Reaction

有了这个奖项，化学合成计划是支持教授凯M。Brummond在匹兹堡大学开发了分子内扩散-Diels-桤木（IMDDA）反应，以制备萘衍生物和苯并稠合杂环。 这些物质是用于各种应用的有价值的结构单元，但不容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制备以前无法获得的芳香族化合物，其具有应用于有机发光二极管、液晶、成像剂、手性配体和药物的潜力。将探索可持续和绿色替代品，用于制备作为IMDDA前体的苯乙烯基化合物。从IMDDA加合物中热除去氢气以形成芳族化合物为基于试剂的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合成有机化学方面的最新培训，该项目具有重大的潜在科学影响。 在IMDDA中，系留的苯乙烯基和炔基的[2+4]环加成之后是分子氢的热损失，以提供萘衍生物。这项研究预计将显着扩大IMDDA的范围和实用性，使该反应成为制备官能化萘，二氢萘和苯并稠合杂环的可行途径。此外，将开发IMDDA反应条件以控制选择性和可预测地形成芳族或二氢芳族产物的发散反应途径。通过机理研究，将更好地理解无受体脱氢反应，并将应用计算洞察力来指导反应条件，底物和靶的选择。最后，预期这些热反应条件将与多种官能度相容，并且因此适合于制备高度取代的和二取代基官能化的萘和其它有价值的芳族化合物。

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.