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Retro-Diels-Alder approach to the synthesis of π-expanded azuliporphyrins and their porphyrinoid aromaticity.

Authors :
Okujima T
Kikkawa T
Nakano H
Kubota H
Fukugami N
Ono N
Yamada H
Uno H
Source :
Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2012 Oct 01; Vol. 18 (40), pp. 12854-63. Date of Electronic Publication: 2012 Aug 22.
Publication Year :
2012

Abstract

Bicyclo[2.2.2]octadiene (BCOD) fused azuliporphyrins were synthesized by 3+1 porphyrin synthesis of azulitripyrranes with diformylpyrroles. Subsequent retro-Diels-Alder reaction of the BCOD-fused azuliporphyrins afforded azulibenzo-, azulidibenzo-, and azulitribenzoporphyrins 1-5. NMR and UV/Vis spectra, as well as nucleus-independent chemical shift (NICS) calculations revealed that 1-5 and their diprotonated dications exhibit relatively low porphyrinoid aromaticity, which was dependent on the position and number of fused benzene rings present.<br /> (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Details

Language :
English
ISSN :
1521-3765
Volume :
18
Issue :
40
Database :
MEDLINE
Journal :
Chemistry (Weinheim an der Bergstrasse, Germany)
Publication Type :
Academic Journal
Accession number :
22915443
Full Text :
https://doi.org/10.1002/chem.201201399