Preparative Electron Transfer Photochemistry

制备型电子转移光化学

• 批准号: 0130943
• 负责人: Patrick Mariano
• 金额: $ 37.6万
• 依托单位: University of New Mexico
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-03-01 至 2005-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0130943&HistoricalAwards=false
• 关键词: Preparative; Electron; Transfer; Photochemistry

The emphasis of this work is on the development of new single electron transfer initiated photochemical reactions. Photochemical group transfer reactions which result from the formation of reactive dipolar intermediates will be investigated in detail. Photochemical preparation and trapping of 1,3 dipoles such as azomethine and carbonyl ylides will be studied as will 1,4 dipole forming and trapping reactions of alpha ketoamides and alpha ketoesters. Single electron transfer initiated photomacrocyclization reactions will also be studied, first using phthalimides. Photomacrocyclization of phthalimides will be used to determine the factors which govern efficiencies and regioselectivities of photocyclizations then that information will be applied to macrocyclic polyether, polyamide and polypeptide syntheses. With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. Patrick S. Mariano of the Department of Chemistry at the University of New Mexico. Dr. Mariano will explore photochemical group transfer, cyclization and redox reactions. The photocyclization reactions studied will serve as the foundation for new polyether, polyamide, and polypeptide syntheses and thus have potential applications for the preparation of antibiotics and other pharmaceuticals. Discovery of selective, photochemical amine oxidation reactions has potential applications in the design of inactivators of flavoenzymes such as monoamine oxidase. Students trained during the course of this work will be broadly trained in preparative organic chemistry and preparative photochemistry and gain skills needed by the pharmaceutical industry.

本工作的重点是发展新的单电子转移引发的光化学反应。对反应性偶极中间体形成的光化学基团转移反应进行了详细的研究。将研究1,3偶极子如亚甲胺和羰基酰的光化学制备和捕获，以及α酮酰胺和α酮酯的1,4偶极子形成和捕获反应。单电子转移引发的光大环化反应也将被研究，首先使用邻苯二甲酸亚胺。邻苯二甲酸亚胺的光环化将用于确定影响光环化效率和区域选择性的因素，然后这些信息将应用于大环聚醚、聚酰胺和多肽的合成。有了这个奖项，有机和大分子化学计划支持新墨西哥大学化学系的帕特里克·s·马里亚诺博士的研究。Mariano博士将探讨光化学基团转移、环化和氧化还原反应。所研究的光环化反应将为新的聚醚、聚酰胺和多肽的合成奠定基础，因此在制备抗生素和其他药物方面具有潜在的应用前景。选择性光化学胺氧化反应的发现在单胺氧化酶等黄酮类酶灭活剂的设计中具有潜在的应用价值。在本课程中训练的学生将在制备有机化学和制备光化学方面得到广泛的训练，并获得制药工业所需的技能。