Porphyrin architectures bearing functionalized xanthene spacers
Porphyrin architectures bearing functionalized xanthene spacers
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DOI：
10.1021/jo016095k
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发表时间：
2002-02-22
影响因子：
3.6
通讯作者：
Nocera, DG
中科院分区：
文献类型：
--
作者：
Chang, CJ;Yeh, CY;Nocera, DG
提出了一种在氧杂蒽平台上构建具有氢键的配位卟啉结构的模块化合成策略。收敛的方法是基于一个咕吨酯的构建块，这是很容易获得的一个多克规模与最小的纯化。在标准Lindsey条件下，用各种芳基醛和吡咯处理这种咕吨衍生物，提供了一个带有单个官能化咕吨间隔基的内消旋取代的卟啉家族。大环化后氢键合成子的直接修饰顺利进行，以提供具有多种共面官能度（例如，羧酸、酯、酰胺）。带有两个反式官能化的咕吨间隔基的卟啉通过咕吨双酯与容易获得的5-芳基取代的二吡咯甲烷如5-均三甲苯基二吡咯甲烷的MacDonald [2 + 21]缩合制备，在色谱分离后得到纯的α，α-和α，β-卟啉阻转异构体。这种合成方法的多功能性为使用这些和相关模板研究小分子的质子偶联活化提供了有趣的机会。
A modular synthetic strategy for the construction of cofacial porphyrin architectures bearing hydrogen-bond synthons on a xanthene platform is presented. The convergent approach is based on a xanthene aldehyde-ester building block that is easily obtainable on a multigram scale with minimal purification. Treatment of this xanthene derivative with a variety of aryl aldehydes and pyrrole under standard Lindsey conditions affords a family of meso-substituted porphyrins bearing a single functionalized xanthene spacer. Direct modification of the hydrogen-bond synthon after macrocyclization proceeds smoothly to furnish porphyrin systems with a variety of cofacial functionalities (e.g., carboxylic acid, ester, amide). Porphyrins bearing two trans-functionalized xanthene spacers are prepared by the MacDonald [2 + 21 condensation of the xanthene aldehyde-ester with readily available 5-aryl-substituted dipyrromethanes such as 5-mesityldipyrromethane to afford the pure alpha,alpha- and alpha,beta-porphyrin atropisomers after chromatographic separation. The versatility of this synthetic method offers intriguing opportunities for the use of these and related templates for the study of proton-coupled activation of small molecules.