Macrocycle Contraction and Expansion of a Dihydrosapphyrin Isomer

Cyclization of a pentapyrrane with two terminal β-linked pyrroles afforded a dihydrosapphyrin isomer (1) with the pyrroles linked in a unique β,α–α,β mode, which was rather reactive, and thus it readily underwent a ring-contracted rearrangement to a pyrrolyl norrole (2), and succeeding ring expansio...

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Veröffentlicht in:Journal of the American Chemical Society 2013-12, Vol.135 (51), p.19119-19122
Hauptverfasser: Xie, Yongshu, Wei, Pingchun, Li, Xin, Hong, Tao, Zhang, Kai, Furuta, Hiroyuki
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Sprache:eng
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Zusammenfassung:Cyclization of a pentapyrrane with two terminal β-linked pyrroles afforded a dihydrosapphyrin isomer (1) with the pyrroles linked in a unique β,α–α,β mode, which was rather reactive, and thus it readily underwent a ring-contracted rearrangement to a pyrrolyl norrole (2), and succeeding ring expansion to a terpyrrole-containing isosmaragdyrin analogue (4). 1, 2, and 4 contain the internal ring pathways with a minimum of 17, 15, and 16 atoms, respectively. 1, 2, and 4 are almost nonfluorescent, whereas the complex of 2 with Zn2+ shows a distinct NIR emission peak at 741 nm. The unprecedented pyrrole transformation chemistry by confusion approach is illustrated.
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja4112644