对亚苯基桥连双卟啉衍生的七元环/八元环稠合双卟啉或螺五元环桥连二氢卟吩
Heptagon/Octagon-Fused Diporphyrins or Spiro-Pentagon-Bridged Dichlorin from p-Terphenylene-Bridged Diporphyrin.
作者信息
Lin Peng, Xiong Shugang, Rao Yutao, Xu Ling, Zhou Mingbo, Yin Bangshao, Osuka Atsuhiro, Song Jianxin
机构信息
Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, 410081, P. R. China.
出版信息
Chem Asian J. 2023 Mar 14;18(6):e202300018. doi: 10.1002/asia.202300018. Epub 2023 Feb 13.
Intramolecular fusion reactions of a p-terphenylene-bridged Ni porphyrin dimer gave different products, depending upon reaction conditions. Oxidation with Fe(OTf) provided syn- and anti-doubly heptagon-fused Ni porphyrin dimers showing enlarged π-electronic networks, probably via a radical mechanism, while treatment with methanesulfonic acid provided a spiro-pentagon-bridged Ni chlorin dimer via acid-catalyzed Friedel-Crafts type cyclization. Further, a doubly octagon-fused Ni porphyrin dimer was synthesized via a sequence of double meso-formylation, reduction to corresponding diol, and BF -catalyzed cyclization.
对三联苯桥连的镍卟啉二聚体的分子内融合反应会产生不同的产物，这取决于反应条件。用三氟甲磺酸铁氧化可得到顺式和反式双七元环稠合的镍卟啉二聚体，其显示出扩大的π电子网络，可能是通过自由基机制实现的，而用甲磺酸处理则通过酸催化的傅克型环化反应得到螺五元环桥连的镍二氢卟吩二聚体。此外，通过双中位甲酰化、还原为相应的二醇以及BF催化的环化反应序列合成了双八元环稠合的镍卟啉二聚体。
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