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Synthesis 2011(17): 2709-2720  
DOI: 10.1055/s-0030-1260141
FEATUREARTICLE
© Georg Thieme Verlag Stuttgart ˙ New York

Lewis Acid or Alkyl Halide Promoted Rearrangements of Phosphor- and Phosphinimidates to N,N-Disubstituted Phosphor- and Phosphinamidates

Ina Wilkening, Giuseppe del Signore, Wiebke Ahlbrecht, Christian P. R. Hackenberger*
Freie Universität Berlin, Institut für Chemie und Biochemie, Takustr. 3, 14195 Berlin, Germany
Fax: +49(30)83852551; e-Mail: hackenbe@chemie.fu-berlin.de;
Further Information

Publication History

Received 4 May 2011
Publication Date:
27 July 2011 (online)

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Abstract

In this paper, we describe the synthesis of N,N-disubstituted phosphor- and phosphinamidates via alkyl halide or Lewis acid catalyzed rearrangements of phosphor- or phosphinimidates. Furthermore, we introduce a novel one-pot procedure for the synthesis of N,N-disubstituted phosphoramidates which prevents the isolation of potentially explosive alkyl azide derivatives. In this reaction sequence, several alkyl halides are converted in situ into the corresponding azides and reacted with phosphites to generate phosphorimidates. Final addition of a catalytic amount of Lewis acid to the mixture affords the N,N-disubstituted phosphoramidates in good to excellent overall yields.

1 Introduction

2 Synthesis of N,N-Disubstituted Phosphor- and Phosphinamidates

2.1 Alkyl Halide Catalyzed Rearrangement of Phosphin- and Phosphorimidates

2.2 Lewis Acid Catalyzed Rearrangement of Phosphin- and Phosphorimidates

2.3 One-Pot Procedure for the Formation of N,N-Disubstituted Phosphoramidates from Alkyl Halides

3 Conclusion

Key words

Staudinger reaction - phosphorimidate rearrangement - phosphoramidates - phosphinamidate - one-pot procedure - Lewis acid catalysis

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