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.

通过该奖项，化学综合计划正在支持匹兹堡大学的Kay M. Brummond教授，以开发分子内二氢化二氧化物 - 碱（IMDDA）的反应，以制备萘衍生物和苯并融合的杂环。 这些物质是各种应用的宝贵构件，但通过已知的合成方法不容易获得。 IMDDA的操作简单性和可伸缩性有可能促进先前无法访问的芳族化合物制备，并有可能应用有机光二极管，液晶，成像剂，手性配体和药物。将探索用于制备苯乙烯化合物作为IMDDA前体的可持续和绿色替代方法。从IMDDA加合物中氢气的热去除以形成芳香化合物，为基于试剂的氧化方案提供了环境良性的替代方案。这项研究将为研究生的合成有机化学方面的最先进的培训，该项目具有巨大的科学广泛影响。 在IMDDA中，[2+4]绑扎型苯基和烷基基团的环载细分之后是分子氢的热损失，以提供萘衍生物。预计这项研究将显着扩大IMDDA的范围和效用，使该反应成为准备功能化的萘，二羟苯二甲酰甲烯烃和苯甲酸苯甲酸苯二甲酸盐和苯并fused的杂环的可行途径。此外，将开发IMDDA反应条件，以控制芳族或二氢芳族产物的选择性和可预测形成的不同反应途径。通过机械研究，将开发出对受体无脱氢反应的更好理解，并将应用计算洞察力来指导反应条件，底物和靶标的选择。最后，预计这些热反应条件将与各种功能兼容，因此可以与高度取代和功能多样化的萘和其他有价值的芳族化合物的制备。