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 journalArticle

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.
@article{fb371fd7f1a54c5b9a61fcca8a65e7ed,
title = "Double Ring Expansion from an Aromatic [18]Porphyrin(1.1.1.1) to an Antiaromatic [20]Porphyrin(2.1.2.1)",
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.",
author = "Masataka Umetani and Takayuki Tanaka and Taeyeon Kim and Dongho Kim and Atsuhiro Osuka",
year = "2016",
month = "7",
day = "4",
doi = "10.1002/anie.201602874",
language = "English",
volume = "55",
pages = "8095--8099",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "John Wiley and Sons Ltd",
number = "28",

}

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 journalArticle

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

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.

UR - http://www.scopus.com/inward/record.url?scp=84971328556&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84971328556&partnerID=8YFLogxK

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 -