Preparative Electron Transfer Photochemistry

本工作的重点是开发新的单电子转移引发的光化学反应。我们将详细研究由反应性偶极中间体形成的光化学基团转移反应。将研究1，3偶极子的光化学制备和捕获，如甲亚胺和羰基叶立德，以及α-酮酰胺和α-酮酯的1，4偶极形成和捕获反应。还将研究单电子转移引发的光环化反应，首先使用邻苯二甲酰亚胺。邻苯二甲酰亚胺的光大环化反应将被用来确定控制光环化反应效率和区域选择性的因素，然后这些信息将被应用于大环聚醚、聚酰胺和多肽的合成。通过这一奖项，有机和高分子化学项目支持了新墨西哥大学化学系的帕特里克·S·马里亚诺博士的研究。马里亚诺博士将探索光化学基团转移、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，从而在抗生素和其他药物的制备方面具有潜在的应用前景。选择性的光化学胺氧化反应的发现在黄素酶的灭活剂的设计中具有潜在的应用，例如单胺氧化酶。在这项工作过程中培训的学生将接受制备性有机化学和制备性光化学的广泛培训，并获得制药业所需的技能。

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.