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Synthesis 2012(3): 323-350  
DOI: 10.1055/s-0031-1289665
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Rhodium-Catalyzed [2+2+2] Cycloaddition of Alkynes for the Synthesis of Substituted Benzenes: Catalysts, Reaction Scope, and Synthetic Applications

Yu Shibata, Ken Tanaka*
Department of Applied Chemistry, Graduate School of Engineering, Tokyo University of Agriculture and Technology, Koganei, Tokyo 184-8588, Japan
Fax: +81(42)3887037; e-Mail: tanaka-k@cc.tuat.ac.jp;
Further Information

Publication History

Received 30 September 2011
Publication Date:
03 January 2012 (online)

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Abstract

The transition-metal-catalyzed [2+2+2] cycloaddition of alkynes is a useful and atom-economical method for the synthesis of substituted benzenes. This comprehensive review covers the [2+2+2]-cycloaddition reactions catalyzed by rhodium complexes. Applications of the rhodium-catalyzed [2+2+2] cycloaddition in the synthesis of functional organic compounds are also described.

1 Introduction

2 [2+2+2]-Cycloaddition Reactions Catalyzed by Neutral Rhodium Complexes

2.1 Intermolecular Reactions

2.2 Intramolecular Reactions

3 [2+2+2]-Cycloaddition Reactions Catalyzed by Cationic Rhodium Complexes

3.1 Intermolecular Reactions

3.2 Intramolecular Reactions

4 Synthetic Applications

4.1 Synthesis of Cyclophanes

4.2 Synthesis of Biaryls

4.3 Synthesis of Organophosphorus Compounds

4.4 Synthesis of Helicene-Like Molecules

4.5 Synthesis of Complex Biologically Active Compounds

4.6 Synthesis of Organic Materials

5 Summary and Outlook

Key words

alkynes - benzenes - catalysis - cycloaddition - rhodium

4

For a review of the transition-metal-catalyzed enantio-selective [2+2+2]-cycloaddition reactions for the synthesis of axially chiral biaryls, see ref. 1i.

133

For our account of the cationic rhodium(I)-biaryl bisphosphine complex catalyzed [2+2+2]-cycloaddition reactions, see ref. 1p.