Grover Vratta, Ravikanth Mangalampalli
Department of Chemistry, Indian Institute of Technology, Powai, Mumbai, 400076, India.
Top Curr Chem (Cham). 2025 Jun 2;383(2):22. doi: 10.1007/s41061-025-00506-y.
Dipyrroethanes/dipyrroethenes (DPEs) containing two pyrroles connected by two meso sp/sp carbons are very useful precursors for the synthesis of very novel porphyrinoids. Dipyrromethanes/dipyrromethenes (DPMs) that consist of two pyrrole rings connected via one meso sp/sp carbon are the most popular precursors for the synthesis of several types of porphyrinoids. Dipyrromethanes/dipyrromethenes can be readily prepared by condensing aldehyde and pyrrole under acid-catalyzed conditions, whereas dipyrroethenes (DPEs) require a few skilled synthetic steps to be obtained in good quantities. Especially, dipyrroethenes exist in E/Z-isomeric mixtures but their separation is not required for the synthesis of porphyrinoids. In the last decade, DPEs have been used as key precursors to synthesize contracted porphyrins such as triphyrins(2.1.1), porphyrin isomers such as porphycene(2.0.2.0), and several expanded porphyrins. This review describes different methods available for the synthesis of 5,6-di(alkyl/aryl/heteroaryl) dipyrroethanes/dipyrroethenes and their use in the synthesis of different porphyrinoids ranging from contracted porphyrinoids to expanded porphyrinoids. The structure, reactivity, and physico-chemical properties of various porphyrinoids which were synthesized from DPEs are also discussed.
含有通过两个内消旋sp/sp碳相连的两个吡咯的二吡咯乙烷/二吡咯乙烯（DPEs）是合成非常新颖的卟啉类化合物的非常有用的前体。由通过一个内消旋sp/sp碳相连的两个吡咯环组成的二吡咯甲烷/二吡咯亚甲基（DPMs）是合成几种卟啉类化合物最常用的前体。二吡咯甲烷/二吡咯亚甲基可以通过在酸催化条件下使醛和吡咯缩合轻松制备，而二吡咯乙烯（DPEs）则需要一些熟练的合成步骤才能大量获得。特别是，二吡咯乙烯以E/Z异构体混合物形式存在，但它们的分离对于卟啉类化合物的合成不是必需的。在过去十年中，DPEs已被用作关键前体来合成缩合卟啉，如三卟啉（2.1.1）、卟啉异构体如卟吩（2.0.2.0）以及几种扩展卟啉。本综述描述了可用于合成5,6-二（烷基/芳基/杂芳基）二吡咯乙烷/二吡咯乙烯的不同方法，以及它们在从缩合卟啉类化合物到扩展卟啉类化合物的不同卟啉类化合物合成中的应用。还讨论了由DPEs合成的各种卟啉类化合物的结构、反应性和物理化学性质。
