m-Pyrenisubporphyrins and Their BIII Complexes and Reduced Congeners

Yi Wang; Le Liu; Yutao Rao; Ling Xu; Mingbo Zhou; Bangshao Yin; Atsuhiro Osuka; Jianxin Song

doi:10.1002/asia.202500693

m-Pyrenisubporphyrins and Their B^III Complexes and Reduced Congeners

Chem Asian J. 2025 Jun 10:e00693. doi: 10.1002/asia.202500693. Online ahead of print.

Authors

Yi Wang¹, Le Liu¹, Yutao Rao¹, Ling Xu¹, Mingbo Zhou¹, Bangshao Yin¹, Atsuhiro Osuka¹, Jianxin Song¹

Affiliation

¹ Key Laboratory of Chemical Biology and Traditional Chinese Medicine, Ministry of Educational 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, China.

PMID: 40492367
DOI: 10.1002/asia.202500693

Abstract

m-Pyrenisubporphyrins were synthesized by Pd-catalyzed cross-coupling of α,α'-diboryl-m-pyrenitripyrrane with 9,10-bis(1,1-dibromomethylenyl)anthracene followed by oxidation with DDQ. Reaction of the m-pyrenisubporphyrin with BBr₃ and triethylamine gave a B-hydroxy complex and an oxygen-atom-inserted product. Reaction of the m-pyrenisubporphyrin with PhBCl₂ and triethylamine gave a B-phenyl complex. These m-pyrenisubporphyrins show red-shifted absorption bands, reflecting the incorporated pyrene segment, but are all nonaromatic. Reduction of m-pyrenisubporphyrin with p-tosylhydrazide and K₂CO₃ gave m-pyrenisubchlorin and m-pyrenisubbacteriochlorin, depending upon the reaction conditions. These reduced products have also been shown to be nonaromatic by the low-field shifted chemical shifts of the inner pyrrolic protons, broad and non-structured absorption bands, and small NICS values.

Keywords: BIII porphyrinoid; Carbaporphyrin; Pyrenisubporphyrin; Subbacteriochlorin; Subchlorin.

Abstract

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