Synthetic Pyridinium Salt Photochemistry

合成吡啶盐光化学

• 批准号: 0506758
• 负责人: Patrick Mariano
• 金额: $ 36万
• 依托单位: University of New Mexico
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2005
• 资助国家: 美国
• 起止时间: 2005-08-01 至 2008-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0506758&HistoricalAwards=false
• 关键词: Synthetic; Pyridinium; Salt; Photochemistry

This research program addresses the development of novel synthetic methods that can be applied to the design of concise routes for the preparation of biomedically important targets. The investigations build on an intriguing pyridinium salt photocyclization reaction, discovered nearly 30 years ago, which will be transformed into a potent methodology for the stereocontrolled synthesis of highly functionalized aminocyclopentenes. The generality of this photocyclization reaction will be probed through an exploration of the photochemistry of fused-pyridinium and polycondensed N-heteroaromatic salts. Absolute stereochemical control of the pyridinium salt photocyclization reactions by N-linked carbohydrate auxiliaries and chiral tethers will be also investigated. Stereocontrolled pyridinium salt photocyclization reactions will be used as key steps in short sequences for the synthesis of the potent trehalase inhibitor (+)-trehazoline, the proteasome inhibitor (+)-lactacystin, and the glycosidase inhibitors (+)-castanospermine, uniflorine-A and related polyhydroxylated indolizidines and quinolizidines.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. Professor Mariano and his students are exploring light-driven ("photochemical") reactions as potential tools to effect the controlled synthesis of various classes of organic molecules. The investigation concentrates on synthetic methodology development, but it is more broadly designed to address issues that relate to the synthesis of biomedically important targets and the chemistry of the high energy intermediate molecules formed in photochemical processes. General contributions will be made to the field of synthetic organic chemistry, while equally significant is the impact that the studies will have on chemical education, with this project providing a broad, comprehensive foundation for students.

这项研究计划致力于开发新的合成方法，这些方法可以应用于设计简明的路线，以制备具有重要生物医学意义的目标。这些研究建立在近30年前发现的耐人寻味的吡啶盐光环化反应的基础上，该反应将转化为一种有效的方法学，用于立体控制合成高度官能化的氨基环戊烯。通过对稠合吡啶盐和聚缩合N-杂芳盐的光化学的探索，探讨了这种光环化反应的共性。还将研究N-连接的碳水化合物助剂和手性链条对吡啶盐光环化反应的绝对立体化学控制。立体受控的吡啶盐光环化反应将被用作短序列中的关键步骤，用于合成有效的海藻糖酶抑制剂(+)-三唑啉、蛋白酶体抑制剂(+)-lactacystin，以及糖苷酶抑制剂(+)--蓖麻籽碱、Unflorine-A以及相关的多羟基吲哚和喹啉类化合物。凭借这一奖项，有机和高分子化学计划支持新墨西哥大学化学系的Patrick S.Mariano博士的研究。马里亚诺教授和他的学生正在探索光驱动(光化学反应)反应，作为实现各种类型有机分子控制合成的潜在工具。这项研究集中在合成方法的开发上，但更广泛的设计是为了解决与生物医学上重要目标的合成以及在光化学过程中形成的高能中间分子的化学有关的问题。该项目将对合成有机化学领域做出一般贡献，同时也将对化学教育产生同样重要的影响，该项目为学生提供了一个广泛的、全面的基础。