Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1)

Masataka Umetani, Takayuki Tanaka, Taeyeon Kim, Dongho Kim, Atsuhiro Osuka

Research output: Contribution to journal › Article

14 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)8095-8099
Number of pages5
JournalAngewandte Chemie - International Edition
Volume55
Issue number28
DOIs
Publication statusPublished - 2016 Jul 4

Fingerprint

Porphyrins
Bearings (structural)
Oxidation
carbon tetrabromide
n-butyllithium
triphenylphosphine

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Umetani, Masataka ; Tanaka, Takayuki ; Kim, Taeyeon ; Kim, Dongho ; Osuka, Atsuhiro. / Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1). In: Angewandte Chemie - International Edition. 2016 ; Vol. 55, No. 28. pp. 8095-8099.
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abstract = "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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Umetani, M, Tanaka, T, Kim, T, Kim, D & Osuka, A 2016, 'Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1)', Angewandte Chemie - International Edition, vol. 55, no. 28, pp. 8095-8099. https://doi.org/10.1002/anie.201602874

Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1). / Umetani, Masataka; Tanaka, Takayuki; Kim, Taeyeon; Kim, Dongho; Osuka, Atsuhiro.

In: Angewandte Chemie - International Edition, Vol. 55, No. 28, 04.07.2016, p. 8095-8099.

Research output: Contribution to journal › Article

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AU - Tanaka, Takayuki

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AU - Kim, Dongho

AU - Osuka, Atsuhiro

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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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Umetani M, Tanaka T, Kim T, Kim D, Osuka A. Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1). Angewandte Chemie - International Edition. 2016 Jul 4;55(28):8095-8099. https://doi.org/10.1002/anie.201602874

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