RUI: Syntheses of Porphyrinic Macrocycles with Altered Core Structures

RUI：核心结构改变的卟啉大环化合物的合成

• 批准号: 0517882
• 负责人: George Geier
• 金额: $ 12.93万
• 依托单位: Colgate University
• 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: 2005-09-01 至 2009-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0517882&HistoricalAwards=false
• 关键词: RUI; Syntheses; Porphyrinic; Macrocycles; Altered

This project focuses on the development and study of synthetic methodology leading to meso-substituted porphyrinic macrocycles with altered core structures. Two structural motifs are a particular focus - the presence of one or more direct bipyrrole linkages as found in macrocycles such as corrole and [34]octaphyrin(1.1.1.0.1.1.1.0), and the presence of an sp3 hybridized meso-position as found in phlorin. Studies of these structural motifs will afford a family of molecules with intriguing structures and properties. In the course of the work, methods for the preparation of bipyrrole building blocks (e.g., diacylbipyrroles and conformationally locked bipyrroles) will be developed, and syntheses of a suite of mesosubstituted porphyrinic macrocycles (e.g., corrole, an octaphyrin, rosarin, a novel N-confused corrole, and phlorin) will be investigated. Promising reactions will be performed on a preparative scale to confirm the results of analytical experiments, as well as to provide suitable quantities for study of selected macrocycle properties (e.g., absorption, emission, stability, metal binding, anion binding).With this Research at Undergraduate Institutions award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. G. Richard Geier III, of the Department of Chemistry at Colgate University. The porphyrin molecule is responsible for reversibly binding oxygen to the oxygen storage and transport proteins, hemoglobin and myoglobin. Porphyrin-like molecules with altered core structures are of current interest, permitting experimental scrutiny of important and fundamental chemical questions, including aromaticity, metal binding, anion binding, photochemical reactions, electrochemical reactions, and catalysis. Studies of a wide variety of porphyrinic macrocycles add to our collective understanding of their properties, and to the potential for their application in industry and medicine. Key to these efforts is the development and refinement of synthetic methodology for the preparation of porphyrinic species. Professor Geier and his students are developing synthetic methods allowing the systematic exploration of the effects of ring expansion, contraction, isomerization, heteroatom modification, and other structural changes on the structures and chemistry of porphyrinic species. These studies also play a valuable role in training a large and diverse group of undergraduate students in the techniques of chemical synthesis and analysis.

本项目的重点是开发和研究导致具有改变的核心结构的中位取代卟啉大环化合物的合成方法。两个结构基序是一个特别的焦点-一个或多个直接联吡咯键的存在下，发现在大环，如咔咯和[34]octaphyrin（1.1.1.0.1.1.1.0），并存在一个sp3杂交的中位发现根皮素。这些结构基序的研究将提供一个家庭的分子与有趣的结构和性能。在工作过程中，制备联吡咯结构单元（例如，二酰基联吡咯和构象锁定的联吡咯），并合成一系列中位取代的卟啉大环（例如，corrole，octaphyrin，rosarin，novel N-confused corrole，phlorin）。有希望的反应将在制备规模上进行，以确认分析实验的结果，以及为研究所选的大环性质（例如，吸收，发射，稳定性，金属结合，阴离子结合）。有了这个研究在本科院校奖，有机和高分子化学计划是支持博士G。科尔盖特大学化学系的理查德·盖尔三世说。卟啉分子负责将氧可逆地结合到氧储存和运输蛋白质、血红蛋白和肌红蛋白。具有改变的核心结构的卟啉样分子是当前感兴趣的，允许对重要和基本的化学问题进行实验审查，包括芳香性、金属结合、阴离子结合、光化学反应、电化学反应和催化。各种各样的卟啉大环化合物的研究增加了我们对其性质的集体理解，以及它们在工业和医学中的应用潜力。这些努力的关键是发展和完善的合成方法制备卟啉物种。Geier教授和他的学生正在开发合成方法，允许系统地探索扩环，收缩，异构化，杂原子修饰和其他结构变化对卟啉物种的结构和化学的影响。这些研究也发挥了宝贵的作用，在培养一个大的和不同的本科生群体在化学合成和分析的技术。