meso-aryl-substituted expanded porphyrins
meso-aryl-substituted expanded porphyrins
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DOI：
10.1021/ja0106624
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发表时间：
2001-07-25
影响因子：
15
通讯作者：
Osuka, A
中科院分区：
文献类型：
--
作者：
Shin, JY;Furuta, H;Osuka, A
近年来，由于其光学、电化学和配位特性，扩展的卟啉已成为一类有前途的分子。 1 持续的合成努力最终开发出了多种含吡咯大环化合物。 2 尽管如此，具有四个以上吡咯亚基的内消旋芳基取代的扩展卟啉的合成仍然是一个重要的课题，因为从内消旋四芳基卟啉的广泛使用来看，它们可以被视为扩展卟啉家族的“合法”成员。最近在 Rothemund 型卟啉合成中同时形成变体（例如 Corrole 1、3 N-混淆卟啉 2、4 和 sapphyrin 35）的发现促使我们重新研究环化反应（图 1）。在此，我们报道了通过五氟苯甲醛和吡咯的酸催化缩合，轻松合成了一系列内消旋芳基取代的扩大卟啉。在改进的Lindsey条件下合成了一系列内消旋芳基取代的扩大卟啉，在相对较高的浓度下合成了一系列内消旋芳基取代的扩大卟啉，两种反应物在CH2Cl2和BF3，OEt2（4.2 mM）中的反应物浓度均为67 mM。用DDQ氧化后，通过硅胶柱重复层析，分离出不同的产物，包括卟啉4（11∼12%）、N-融合五菲林NFP5 7（14∼15%）、六菲林68（16∼20%）、七菲林79（4∼5%）、八菲林8（5∼6%）、九萘菲林9（2∼ 3%），甚至更高的同系物，10 根据其各自的 1H NMR 和 FAB-MS 数据判断（方案 1）。
In recent years expanded porphyrins have emerged as a promising class of molecules in light of their optical, electrochemical, and coordination properties. 1 Continuing synthetic efforts have culminated in the developments of a variety of large pyrrole-containing macrocycles. 2 Nevertheless, the synthesis of meso-aryl-substituted expanded porphyrins with more than four pyrrolic subunits still remains an important subject, since they could be considered as the “legitimated” members of the expanded porphyrin family as judged from the wide use of meso-tetraaryl porphyrins. Recent findings of concurrent formation of variants such as corrole 1, 3 N-confused porphyrin 2, 4 and sapphyrin 35 in the Rothemund-type porphyrin synthesis have tempted us to reinvestigate the cyclization reaction (Chart 1). Herein, we report a facile synthesis of a series of meso-aryl-substituted expanded porphyrins by the acid-catalyzed condensation of pentafluorobenzaldehdye and pyrrole.A series of meso-aryl-substituted expanded porphyrins were synthesized under the modified Lindsey conditions, 6 at relatively high concentration, 67 mM in both the reactants in CH2Cl2 with BF3 ‚OEt2 (4.2 mM). After the oxidation with DDQ, repeated chromatography over a silica gel column led to isolation of distinct products including porphyrin 4 (11∼ 12%), N-fused pentaphyrin NFP5 7 (14∼ 15%), hexaphyrin 68 (16∼ 20%), heptaphyrin 79 (4∼ 5%), octaphyrin 8 (5∼ 6%), nonaphyrin 9 (2∼ 3%), and even higher homologues, 10 as judged by their respective 1H NMR and FAB-MS data (Scheme 1).