Synthetic Pyridinium Salt Photochemistry

该研究计划致力于开发新的合成方法，这些方法可用于设计用于制备生物医学重要目标的简洁路线。这些研究建立在近30年前发现的一种有趣的吡啶盐光环化反应的基础上，该反应将转化为立体控制合成高度官能化的氨基环戊烯的有效方法。这种光环化反应的一般性将探讨通过探索的光化学的稠合吡啶和缩聚N-杂芳族盐。绝对的立体化学控制的吡啶鎓盐的光环化反应的N-连接的碳水化合物助剂和手性栓也将进行研究。立体控制的吡啶盐光环化反应将被用作合成有效的海藻糖酶抑制剂（+）-海藻唑啉、蛋白酶体抑制剂（+）-lactacystin和糖苷酶抑制剂（+）-栗精胺、uniflorine-A和相关的多羟基吲哚嗪和喹嗪的短序列中的关键步骤。有了这个奖项，有机和大分子化学项目支持帕特里克S.新墨西哥州大学化学系的马里亚诺说。Mariano教授和他的学生正在探索光驱动（“光化学”）反应作为影响各种有机分子受控合成的潜在工具。调查集中在合成方法的发展，但它更广泛地设计，以解决与生物医学重要目标的合成和在光化学过程中形成的高能中间分子的化学有关的问题。一般的贡献将在合成有机化学领域，而同样重要的是，该研究将对化学教育的影响，该项目为学生提供了广泛，全面的基础。

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.