TY - JOUR
T1 - Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1)
AU - Umetani, Masataka
AU - Tanaka, Takayuki
AU - Kim, Taeyeon
AU - Kim, Dongho
AU - Osuka, Atsuhiro
N1 - Publisher Copyright:
© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
PY - 2016/7/4
Y1 - 2016/7/4
N2 - Double ring expansion from a 5,15-diarylporphyrin to a 5,16-diaryl-10,11,21,22-tetradehydro[20]porphyrin(2.1.2.1) occurred through a reaction sequence consisting of oxidation with PbO2to 5,15-dioxoporphodimethene, a Corey–Fuchs reaction with tetrabromomethane in the presence of triphenylphosphine, and Fritsch–Buttenberg–Wiechell rearrangement triggered by tert-butyllithium. The obtained tetradehydro[20]porphyrin(2.1.2.1) and its mono- and dihydrogenated congeners exhibited 20 π antiaromatic character, whereas overhydrogenated congeners bearing a saturated bridge were nonaromatic owing to disrupted π conjugation.
AB - Double ring expansion from a 5,15-diarylporphyrin to a 5,16-diaryl-10,11,21,22-tetradehydro[20]porphyrin(2.1.2.1) occurred through a reaction sequence consisting of oxidation with PbO2to 5,15-dioxoporphodimethene, a Corey–Fuchs reaction with tetrabromomethane in the presence of triphenylphosphine, and Fritsch–Buttenberg–Wiechell rearrangement triggered by tert-butyllithium. The obtained tetradehydro[20]porphyrin(2.1.2.1) and its mono- and dihydrogenated congeners exhibited 20 π antiaromatic character, whereas overhydrogenated congeners bearing a saturated bridge were nonaromatic owing to disrupted π conjugation.
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U2 - 10.1002/anie.201602874
DO - 10.1002/anie.201602874
M3 - Article
AN - SCOPUS:84971328556
VL - 55
SP - 8095
EP - 8099
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 28
ER -