meso-Trifluoromethyl-substituted expanded porphyrins.
meso-Trifluoromethyl-substituted expanded porphyrins.
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DOI：
10.1002/chem.200600158
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发表时间：
2006-06
期刊：
影响因子：
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通讯作者：
Soji Shimizu;N. Aratani;A. Osuka
中科院分区：
文献类型：
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作者：
Soji Shimizu;N. Aratani;A. Osuka
以2-（2，2，2-三氟-1-羟乙基）吡咯（1）为原料，通过酸催化的一锅缩合反应，合成了一系列三氟甲基取代的内消旋卟啉衍生物，包括N-稠合的[24]五卟啉3、[28]六卟啉4、[32]七卟啉5、[46]十卟啉6和[56]十二卟啉7。除此之外，还得到了卟啉2和两个杯[5]卟啉8和9。[28]用MnO（2）将六卟啉4定量氧化为[26]六卟啉14。这些扩展的卟啉已经通过质谱、（1）H和（19）F NMR光谱和UV/维斯光谱表征。单晶结构已被确定为3，4，6，7，和14。N-稠合的[24]五卟啉3显示出含有三环稠合部分的扭曲结构，其与内消旋芳基取代的对应物类似，而8和9被指示为大致平面构象，其中反式吡咯与sp（3）-杂化的内消旋碳原子相对。[28]-和[26]六卟啉4和14都具有8字形结构。固态结构的decaphyrin 6和dodecaphyrin 7是显着的，表现出新月形构象和分子内的两个螺距螺旋构象，分别。
A series of meso-trifluoromethyl-substituted expanded porphyrins, including N-fused [24]pentaphyrin 3, [28]hexaphyrin 4, [32]heptaphyrin 5, [46]decaphyrin 6, and [56]dodecaphyrin 7, were synthesized by means of an acid-catalyzed one-pot condensation reaction of 2-(2,2,2-trifluoro-1-hydroxyethyl)pyrrole (1) as the first examples bearing meso-alkyl substituents. Besides these products, porphyrin 2 and two calix[5]phyrins 8 and 9 were also obtained. [28]Hexaphyrin 4 was quantitatively oxidized to [26]hexaphyrin 14 with MnO(2). These expanded porphyrins have been characterized by mass spectrometry, (1)H and (19)F NMR spectroscopy, and UV/Vis spectroscopy. The single-crystal structures have been determined for 3, 4, 6, 7, and 14. The N-fused [24]pentaphyrin 3 displays a distorted structure containing a tricyclic fused moiety that is similar to those of meso-aryl-substituted counterparts, whereas 8 and 9 are indicated to take roughly planar conformations with an inverted pyrrole opposite to the sp(3)-hybridized meso-carbon atom. Both [28]- and [26]hexaphyrins 4 and 14 have figure-of-eight structures. Solid-state structures of the decaphyrin 6 and dodecaphyrin 7 are remarkable, exhibiting a crescent conformation and an intramolecular two-pitch helical conformation, respectively.