Mechanistic Study on Ring-Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods
Mechanistic Study on Ring-Contracting Skeletal Rearrangement from Porphycene to Isocorrole by Experimental and Theoretical Methods
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DOI：
10.1002/ejoc.201901659
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发表时间：
2020-01-23
影响因子：
2.8
通讯作者：
Hisaeda, Yoshio
中科院分区：
文献类型：
--
作者：
Koide, Taro;Maeda, Takafumi;Hisaeda, Yoshio
本研究在碱性条件下，采用一锅法研究了八乙基卟啉与两种异咯啉，通过实验和理论研究的对比分析，确定了内消旋-甲酰基和内消旋-游离形式，并提出了反应机理。卟啉的电子接受性质和吡咯环的亚胺-胺转化使其能够与氢氧根离子反应并随后反应得到异可罗。基于该反应，化合物作为配体的价态以及光化学和电化学性质发生了显著变化。
In this study, the ring contracting skeletal rearrangement reaction in one-pot under basic conditions from octaethylporphycene to two types of isocorroles, i.e., the meso-formyl and meso-free forms, was confirmed and the reaction mechanism was proposed by the comparative analyses of the experimental and theoretical studies. The electron accepting nature of the porphycene and imine-amine conversion of pyrrole rings make it possible to react with hydroxide ions and the following reaction to afford isocorroles. Based on this reaction, the valence of the compound as a ligand as well as the photochemical and electrochemical properties were dramatically changed.