Skeletal Rearrangement of Twisted Thia‐Norhexaphyrin: Multiply Annulated Polypyrrolic Aromatic Macrocycles |
| |
Authors: | Qizhao Li Masatoshi Ishida Hiroto Kai Tingting Gu Chengjie Li Xin Li Glib Baryshnikov Xu Liang Weihua Zhu Hans gren Hiroyuki Furuta Yongshu Xie |
| |
Institution: | Qizhao Li,Masatoshi Ishida,Hiroto Kai,Tingting Gu,Chengjie Li,Xin Li,Glib Baryshnikov,Xu Liang,Weihua Zhu,Hans Ågren,Hiroyuki Furuta,Yongshu Xie |
| |
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 pyrrolo1,2]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. |
| |
Keywords: | Aromatizitä t Makrocyclen Porphyrinoide Gerü st-Umlagerungen |
|
|