RUI: Syntheses of Porphyrinic Macrocycles with Altered Core Structures

本项目的重点是开发和研究具有改变核心结构的介取代卟啉大环的合成方法。两个结构基序是特别关注的——在大环如corrole和[34]octaphyrin（1.1.1.0.1.1.1.0）中发现的一个或多个直接双吡咯键的存在，以及在phlorin中发现的sp3杂化介位的存在。对这些结构基序的研究将提供具有有趣结构和性质的分子家族。在工作过程中，将开发制备双酰基双吡咯和构象锁定双吡咯的方法，并将研究一组介取代卟啉大环的合成（例如，corrole，一种八烷基吡咯，rossarin，一种新型n -混淆的corrole和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，并为选定的大环性质（例如，吸收，发射，稳定性，金属结合，阴离子结合）的研究提供合适的数量。有了这个本科院校研究奖，有机和大分子化学项目支持了高尔盖特大学化学系的G. Richard Geier III博士的研究。卟啉分子负责将氧气可逆地结合到氧气储存和运输蛋白质，血红蛋白和肌红蛋白。具有改变核心结构的类卟啉分子是目前的研究热点，它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。对各种卟啉大环的研究增加了我们对它们性质的集体理解，并增加了它们在工业和医学上应用的潜力。这些努力的关键是发展和改进卟啉类化合物的合成方法。Geier教授和他的学生正在开发合成方法，允许系统地探索环膨胀、收缩、异构化、杂原子修饰和其他结构变化对卟啉类物质结构和化学的影响。这些研究在培养大量不同种类的本科学生掌握化学合成和分析技术方面也发挥了重要作用。

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.