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Synlett 2011(16): 2279-2298  
DOI: 10.1055/s-0030-1260316
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© Georg Thieme Verlag Stuttgart ˙ New York

Recent Advances in the Development of Methods for the Preparation of Functionalized Azulenes for Electrochromic Applications

Shunji Ito*a, Taku Shoji*b, Noboru Moritac
a Graduate School of Science and Technology, Hirosaki University, Hirosaki 036-8561, Japan
Fax: +81(172)393568; e-Mail: itsnj@cc.hirosaki-u.ac.jp;
b Department of Chemistry, Faculty of Science, Shinshu University, Matsumoto 390-8621, Japan
c Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan
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Publication History

Received 25 April 2011
Publication Date:
13 September 2011 (online)

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Abstract

Recent advances made in the preparation of aryl- and heteroarylazulenes using transition-metal-catalyzed reactions and azulene electrophilic heteroarylation reactions are described. Emphasis is given to the development of novel azulenyl-substituted metallic reagents. The synthetic routes that utilize these processes as key steps provide straightforward access to functionalized azulene-based advanced materials that possess unique redox properties.

1 Introduction

2 Cross-Coupling Reactions

2.1 Stille Cross-Coupling Reaction

2.2 Suzuki-Miyaura Cross-Coupling Reaction

2.3 Azulenyl-Substituted Lithium and Magnesium Reagents

3 Preparation of Heteroarylazulenes

3.1 Palladium-Catalyzed Heteroarylation

3.2 Electrophilic Heteroarylation at the 1- and 3-Positions

3.3 Reissert-Henze-Type Reaction

3.4 Electrophilic Heteroarylation at the 5- and 7-Positions

3.5 Electrophilic Substitution by ipso-Attack

4 Cycloaddition Routes

4.1 Diels-Alder Reaction

4.2 Cobalt-Mediated Cyclotrimerization

5 Conclusion

Key words

cross-coupling - electrophilic aromatic substitutions - arylations - heterocycles - electron transfer