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Skeletal Rearrangement of Twisted Thia‐Norhexaphyrin: Multiply Annulated Polypyrrolic Aromatic Macrocycles
Author(s) -
Li Qizhao,
Ishida Masatoshi,
Kai Hiroto,
Gu Tingting,
Li Chengjie,
Li Xin,
Baryshnikov Glib,
Liang Xu,
Zhu Weihua,
Ågren Hans,
Furuta Hiroyuki,
Xie Yongshu
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201900010
Subject(s) - thiophene , chemistry , moiety , pyrrole , indolizine , isothiazole , conjugated system , benzothiophene , aromaticity , combinatorial chemistry , stereochemistry , photochemistry , medicinal chemistry , organic chemistry , molecule , polymer
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.