A Dehydro-Diels-Alder Reaction

脱氢-狄尔斯-阿尔德反应

• 批准号: 1465032
• 负责人: Kay Brummond
• 金额: $ 43.5万
• 依托单位: University of Pittsburgh
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-06-15 至 2019-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1465032&HistoricalAwards=false
• 关键词: Dehydro; Diels; Alder; Reaction

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.

通过这一奖项，化学合成计划支持匹兹堡大学的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并稠合杂环。这些物质是各种应用的有价值的构建块，但通过已知的合成方法不易获得。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，并有可能应用于有机发光二极管、液晶、显像剂、手性配体和制药。将探索制备作为IMDDA前体的苯乙烯基化合物的可持续和绿色替代品。热脱除IMDDA加合物中的氢气以形成芳香族化合物，为试剂基氧化提供了一种环境友好的替代方案。这项研究将在一个具有重大潜在科学影响的项目上为研究生提供最先进的合成有机化学培训。在IMDDA中，[2+4]链状苯基和炔基的[2+4]环加成之后是分子氢的热损失，从而提供了一种萘衍生物。这项研究有望显著扩大IMDDA的应用范围和用途，使该反应成为制备官能化的萘、二氢萘和苯并二氢杂环的可行途径。此外，还将开发IMDDA反应条件，以控制用于选择性和可预测地生成芳香族或二氢芳香族产物的发散反应途径。通过机理研究，将加深对无受体脱氢反应的了解，并将应用计算洞察力来指导反应条件、底物和目标的选择。最后，预计这些热反应条件将与各种官能团相容，从而有利于制备高取代和多样化官能化的萘和其他有价值的芳香族化合物。