RUI: Syntheses of Porphyrinic Macrocycles with Altered Core Structures

本项目致力于合成具有改变核心结构的中位取代的卟啉大环的合成方法的开发和研究。有两个结构基序是特别关注的--在大环中存在一个或多个直接的联吡咯键，如在大环中发现的柯拉尔和[34]八氢呋喃(1.1.1.0.1.1.1.0)，以及在邻苯二酚中发现的SP3杂化中位。对这些结构基元的研究将提供一系列具有有趣结构和性质的分子。在这项工作中，将开发制备联吡咯构建块(例如，二酰基联吡咯和构象锁定联吡咯)的方法，并将研究一系列中取代的卟啉大环的合成(例如，考若尔、八氢吡喃、罗沙林、新的N-混杂考若尔和邻苯二酚)。有希望的反应将在制备性规模上进行，以确认分析实验的结果，并为选定的大循环性质(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。凭借这项本科院校研究奖，有机和高分子化学计划将支持高露洁大学化学系G.Richard Geier III博士的研究。卟啉分子负责可逆地将氧与氧储存和运输蛋白、血红蛋白和肌红蛋白结合。具有改变核心结构的类似卟啉的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研究，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。对各种卟啉大环化合物的研究增加了我们对它们的性质的集体了解，并增加了它们在工业和医学中应用的潜力。这些努力的关键是发展和完善制备卟啉物种的合成方法。盖尔教授和他的学生正在开发合成方法，允许系统地探索环扩张、收缩、异构化、杂原子修饰和其他结构变化对卟啉物种结构和化学的影响。这些研究也对培养一大批多样化的本科生的化学合成和分析技术起到了宝贵的作用。

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.