The Cyanamide Moiety, Synthesis and Reactivity

Marie-Hélène Larraufie; Giovanni Maestri; Max Malacria; Cyril Ollivier; Louis Fensterbank; Emmanuel Lacôte

doi:10.1055/s-0031-1289749

Synthesis, Table of Contents

Synthesis 2012; 44(9): 1279-1292
DOI: 10.1055/s-0031-1289749

review

The Cyanamide Moiety, Synthesis and Reactivity

Marie-Hélène Larraufie

^aUPMC Université Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France

,

Giovanni Maestri

^aUPMC Université Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France

,

Max Malacria

^aUPMC Université Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France

,

Cyril Ollivier

^aUPMC Université Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France

,

Louis Fensterbank*

^aUPMC Université Paris 06, Institut Parisien de Chimie Moléculaire (UMR CNRS 7201), 4 place Jussieu, C. 229, 75005 Paris, France

,

Emmanuel Lacôte*

^bICSN CNRS, Avenue de la Terrasse, 91198 Gif-sur-Yvette Cedex, France, Fax: +33(1)44277360; +33(1)69077247 Email: louis.fensterbank@upmc.fr Email: emmanuel.lacote@icsn.cnrs-gif.fr

› Author Affiliations

Abstract

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Abstract

The cyanamide moiety provides many opportunities as a building block for the synthesis of nitrogen-containing heterocycles. This review discusses the reported methods for the preparation of alkyl- and N-acylcyanamides and illustrates their reactivity vis-à-vis nucleophilic additions, cycloadditions, radical chemistry and coordination chemistry.

1 Introduction

2 Biological Relevance of the Cyanamide Moiety

3 Access to Cyanamides

3.1 Cyanation of Amines

3.2 Palladium Catalysis

3.3 Deoxygenation of Isocyanates

3.4 Desulfurization of Thioureas

4 Reactivity of Cyanamides

4.1 Nucleophilic Additions

4.2 Cycloadditions

4.3 Additions to Carbonyl Groups

4.4 Chlorinations and Oxidations with tert-Butyl-N-chlorocyanamide

4.5 Cyanamides as Radical Partners

5 Coordination Chemistry of Cyanamides

6 Conclusion

Key words

cyanamide - cyanation - nitrogen - heterocycles - nitrogen ligands

Full Text

References

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