Palladium-Catalyzed Direct Arylation of Azulene Based on Regioselective C-H Bond Activation

Masahito Murai, Mayu Yanagawa, Masahiro Nakamura, Kazuhiko Takai

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

An efficient synthesis of arylazulenes involving minimal steps was developed. The combination of Pd(OAc)2/XPhos as a catalyst and pivalic acid as an additive was key for the direct arylation of C-H bonds, and the reaction proceeded preferentially at the 1- and 3-positions of azulene, without heteroatom-containing directing groups. Compared with the traditional cross-coupling protocol, the arylation method described here requires fewer steps and uses commercially available synthetic blocks. The degree of conjugation and the optical properties of the resulting azulene conjugates can be adjusted by simple protonation, which allows the current method to be an efficient strategy for exploiting novel azulene-based functional materials.

Original languageEnglish
JournalAsian Journal of Organic Chemistry
DOIs
Publication statusAccepted/In press - 2016

Fingerprint

Palladium
Chemical activation
Functional materials
Protonation
Optical properties
Catalysts
azulene

Keywords

  • Acid-responsive materials
  • Arylation
  • Azulenes
  • C-H bond activation
  • Palladium

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Palladium-Catalyzed Direct Arylation of Azulene Based on Regioselective C-H Bond Activation. / Murai, Masahito; Yanagawa, Mayu; Nakamura, Masahiro; Takai, Kazuhiko.

In: Asian Journal of Organic Chemistry, 2016.

Research output: Contribution to journalArticle

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AB - An efficient synthesis of arylazulenes involving minimal steps was developed. The combination of Pd(OAc)2/XPhos as a catalyst and pivalic acid as an additive was key for the direct arylation of C-H bonds, and the reaction proceeded preferentially at the 1- and 3-positions of azulene, without heteroatom-containing directing groups. Compared with the traditional cross-coupling protocol, the arylation method described here requires fewer steps and uses commercially available synthetic blocks. The degree of conjugation and the optical properties of the resulting azulene conjugates can be adjusted by simple protonation, which allows the current method to be an efficient strategy for exploiting novel azulene-based functional materials.

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