Facile Redox‐Induced Aromatic-Antiaromatic Interconversion of a β‐Tetracyano‐21,23‐Dithiaporphyrin under Ambient Conditions
Facile Redox‐Induced Aromatic-Antiaromatic Interconversion of a β‐Tetracyano‐21,23‐Dithiaporphyrin under Ambient Conditions
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环境条件下β-四氰基-21,23-二硫卟啉的轻松氧化还原诱导芳香族-反芳香族相互转化
DOI：
10.1002/chem.201905823
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发表时间：
2020
期刊：
影响因子：
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通讯作者：
Ogawa Takuji
中科院分区：
文献类型：
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作者：
Yamashita Ken‐ichi;Nakajima Kana;Honda Yusuke;Ogawa Takuji
通过使用β-四氰基-21，23-二硫代卟啉（CN 4S 2 Por）实现了容易的氧化还原诱导的芳香族-反芳香族相互转化。氰基的引入不仅提高了卟啉核的还原电位，而且通过π共轭作用稳定了反芳香异佛尔酮（CN_4S_2 Iph）。即使在环境条件下，在极性溶剂中用肼还原1，2，3，4，6-四氯化萘，也可定量得到1，2，3，4，5，6-四氯化萘。CN 4S 2 Iph保留了几乎平面的构象，并表现出相当大的反芳香性。在非极性溶剂中，1，2，3，4，6-四氯化萘会有氧氧化成1，2，3，4，5，6-四氯化萘。本研究的目的是为理解结构与反芳香性的关系做出贡献。
Facile redox‐induced aromatic–antiaromatic interconversions were accomplished by using β‐tetracyano‐21,23‐dithiaporphyrin (CN4S2Por). Introduced cyano groups not only increased the reduction potential of the porphyrin core but also stabilized the antiaromatic isophlorin (CN4S2Iph) by π conjugation. The reduction of CN4S2Por with hydrazine in polar solvents quantitatively affords CN4S2Iph, even under ambient conditions. CN4S2Iph retains a nearly planar conformation and exhibits considerable antiaromaticity. Aerobic oxidation of CN4S2Iph to CN4S2Por occurs in nonpolar solvents. This study was conducted to contribute to the understanding of the structure–antiaromaticity relationship.