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Synthesis 2011(1): 1-22  
DOI: 10.1055/s-0030-1258294
REVIEW
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium- and Copper-Catalyzed Aryl Halide Amination, Etherification and Thioetherification Reactions in the Synthesis of Aromatic Heterocycles

Jessie E. R. Sadig, Michael C. Willis*
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA, UK
Fax: +44(1865)285002; e-Mail: michael.willis@chem.ox.ac.uk;
Further Information

Publication History

Received 4 August 2010
Publication Date:
12 October 2010 (online)

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Abstract

This article reviews the use of palladium- and copper-catalyzed aryl halide amination, etherification and thioetherification processes in the synthesis of heteroaromatic molecules. The review is structured by the nature of the key C-X bond being formed, and then by heterocycle type. Where applicable individual heterocycles are further divided into syntheses based on intermolecular, intramolecular and cascade processes. In order to limit the length of the article, processes that do not deliver an aromatic heterocycle from the key C-X bond-forming event are excluded. Processes for the functionalization of intact heteroaromatics are also not included.

1 Introduction

2 Carbon-Nitrogen Bond Formation

2.1 Indoles

2.2 Carbazoles

2.3 Benzimidazoles and Benzimidazolones

2.4 Indazoles and Indazolones

2.5 Pyrroles

2.6 Pyrazoles

2.7 Oxazoles

2.8 Quinolones

2.9 Quinazolines, Quinazolinones and Quinazolinediones

2.10 Phenazines

2.11 Cinnolines

3 Carbon-Oxygen Bond Formation

3.1 Benzofurans

3.2 Benzoxazoles

3.3 Isocoumarins

4 Carbon-Sulfur Bond Formation

4.1 Benzothiophenes

4.2 Benzothiazoles

4.3 Oxathioles

5 Conclusion

Key words

palladium catalysis - copper catalysis - aromatic heterocycles - amination - etherification

24

Although the majority of examples described in this approach do not lead directly to an aromatic heterocycle, but to an intermediate, it is included because of its historical relevance to the development of palladium-catalyzed aryl halide amination chemistry in heterocycle synthesis.