Pericyclizations of Conjugated Allenes and Other Polyenes

共轭丙二烯和其他多烯的周环化

• 批准号: 8903581
• 负责人: William Okamura
• 金额: $ 22.44万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-06-15 至 1993-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8903581&HistoricalAwards=false
• 关键词: Pericyclizations; Conjugated; Allenes; Other; Polyenes

+he Synthetic Organic Chemistry Program is supporting the work of Dr. William H. Okamura of the Department of Chemistry at the University of California at Riverside. Dr. Okamura is developing thermal reactions that can be carried out at relatively low temperatures that result in the rapid and efficient formation of complex ring systems. These will provide new routes to the complex materials needed in modern agriculture and industry. The purpose of the research is to carry out exploratory mechanistic and synthetic investigations on the manner in which chiral conjugated allenes and other polyenes participate in carbon-carbon and carbon-hetero atom bond forming pericyclization reactions. The significance of this study is that by systematically evaluating pericyclic and other reactions of polyenes that lead to new bond formation, both mechanistic and theoretical insight into these processes should obtain. Moreover, a detailed understanding of how substituents and substitution patterns affect the stereomechanistic course of pericyclizations should lend information to the synthetic chemist as to how to better develop and design synthetic methods. The synthetic impact of the current proposal is that methodology pertinent to the synthesis of chiral polycyclic building blocks should emerge. The topics include the development of an understanding of pi-facial stereoselectivity effects by substituents on electrocyclic processes and exploration of the scope and limitations of the allene variant of electrocyclizations, ı3,3!-sigmatropic shifts and cycloaddition processes.

+he合成有机化学计划正在支持这项工作 威廉·H博士冈村教授说， 加州大学滨江分校。 冈村博士是 开发热反应，可以在 相对较低的温度，导致快速， 复杂环系的高效形成。 这些将 为现代工业所需的复杂材料提供了新的途径 农业和工业。 本研究的目的是进行探索性的 对如何进行机械和综合研究 手性共轭联烯和其它多烯参与 碳-碳和碳-杂原子键形成 周环化反应 本研究的意义在于 通过系统地评估周环和其他 多烯的反应导致新的键的形成， 对这些过程的机械的和理论的洞察力应该 获得。 此外，详细了解取代基如何 和替代模式影响立体力学过程 应该为合成 化学家如何更好地开发和设计合成 方法. 目前提案的综合影响是， 手性多环化合物的合成方法 积木应该出现。 这些主题包括 发展对π-面立体选择性的理解 取代基对电环化过程的影响， 探索丙二烯变异体的范围和局限性 电环化，<$3，3！-σ向移动， 环加成过程。