Rational Synthesis of Antiaromatic 5,15‐Dioxaporphyrin and Oxidation into β,β‐Linked Dimers,Angewandte Chemie International Edition

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Rational Synthesis of Antiaromatic 5,15‐Dioxaporphyrin and Oxidation into β,β‐Linked Dimers
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2018-07-13 , DOI: 10.1002/anie.201804648
Akihide Nishiyama ₁ , Masaya Fukuda ₁ , Shigeki Mori ₂ , Ko Furukawa ₃ , Heike Fliegl ₄ , Hiroyuki Furuta _{1,

5} , Soji Shimizu _{1,

5}

Affiliation

5,15‐Dioxaporphyrin was synthesized for the first time by a nucleophilic aromatic substitution reaction of a nickel bis(α,α′‐dibromodipyrrin) complex with benzaldoxime, followed by an intramolecular annulation of the α‐hydroxy‐substituted intermediate. This unprecedented molecule is a 20π‐electron antiaromatic system, in terms of Hückel's rule of aromaticity, because lone pair electrons of oxygen atoms are incorporated into the 18π‐electron conjugated system of the porphyrin. A theoretical analysis based on the gauge‐including magnetically induced current method confirmed its antiaromaticity and a dominant inner ring pathway for the ring current. The unique reactivity of 5,15‐dioxaporphyrin forming a β,β‐linked dimer upon oxidation was also revealed.

中文翻译：

抗芳香5,15-二氧杂卟啉的合理合成和氧化成β，β-连接的二聚体

通过镍双（α，α'-二溴二吡啶吡啶）络合物与苯甲醛肟的亲核芳香取代反应，然后分子内环氧化α-羟基取代的中间体，首次合成了5,15-二氧杂卟啉。根据Hückel的芳香定律，这种空前的分子是20π电子抗芳香体系，因为氧原子的孤对电子被并入了卟啉的18π电子共轭体系中。基于包括磁感应电流法的量表的理论分析证实了其具有抗芳香性，并且是环电流的主要内环途径。还揭示了5,15-二氧杂卟啉在氧化时形成β，β-连接的二聚体的独特反应性。

更新日期：2018-07-13

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