Skeletal Rearrangement of Twisted Thia-Norhexaphyrin: Multiply Annulated Polypyrrolic Aromatic Macrocycles

Qizhao Li, Masatoshi Ishida, Hiroto Kai, Tingting Gu, Chengjie Li, Xin Li, Glib Baryshnikov, Xu Liang, Weihua Zhu, Hans Ågren, Hiroyuki Furuta, Yongshu Xie

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

A hybrid thia-norhexaphyrin comprising a directly linked N-confused pyrrole and thiophene unit (1) revealed unique macrocycle transformations to afford multiply inner-annulated aromatic macrocycles. Oxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone triggered a cleavage of the C-S bond of the thiophene unit, accompanied with skeletal rearrangement to afford unique π-conjugated products: a thiopyrrolo-pentaphyrin embedded with a pyrrolo[1,2]isothiazole (2), a sulfur-free pentaphyrin incorporating an indolizine moiety (3), and a thiopyranyltriphyrinoid containing a 2H-thiopyran unit (4). Furthermore, 2 underwent desulfurization reactions to afford a fused pentaphyrin containing a pyrrolizine moiety (5) under mild conditions. Using expanded porphyrin scaffolds, oxidative thiophene cleavage and desulfurization of the hitherto unknown N-confused core-modified macrocycles would be a practical approach for developing unique polypyrrolic aromatic macrocycles.

Original languageEnglish
JournalAngewandte Chemie - International Edition
DOIs
Publication statusE-pub ahead of print - Mar 7 2019

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