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Synthesis 2010(18): 3138-3142  
DOI: 10.1055/s-0030-1258176
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A Practical Synthesis of 1,2-Nitroamines by Michael Addition of N-Nucleophiles to Nitroalkenes

Raphaël Robiette*a, Trieu-Van Trana, Alex Cordib, Bernard Tinanta, Jacqueline Marchand-Brynaert*a
a Institute of Condensed Matter and Nanosciences, Université catholique de Louvain, Place Louis Pasteur 1, 1348 Louvain-la-Neuve, Belgium
Fax: +3210474168; e-Mail: raphael.robiette@uclouvain.be; e-Mail: jacqueline.marchand@uclouvain.be;
b Institut de Recherches Servier, Rue des Moulineaux 11, 92150 Suresnes, France
Further Information

Publication History

Received 20 April 2010
Publication Date:
16 July 2010 (online)

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Abstract

A practical method for the synthesis of α-nitroamines by Michael addition of azide to nitroalkene has been developed. This reaction proceeds in high yields under very mild conditions (phase-transfer catalysis) and is found to be general; good yields are obtained with both aryl and alkyl derivatives as well as with 1,1-di­substituted ones.

Key words

azides - amines - Michael addition - nitroalkenes - nitro­amines

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10

The structure of 3b has been confirmed by X-ray crystallography. The X-ray data have been deposited at the Cambridge Crystallographic Data Centre (deposition number: CCDC 769007). These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033, E-mail: deposit@ccdc.cam.ac.uk].

11

This is consistent with a previous study on addition of benzotriazole on nitroalkene. See ref. 8c.

14

Total conversion was obtained in dichloroethane at 60 ˚C after 5 h.

16

A test reaction showed that the reaction does not proceed in the absence of catalyst.

18

For one example of addition of azide using TMSN3, see 8a.

27

In the case of 4b, the reaction mixture was poured into H2O, extracted with CH2Cl2, and the CH2Cl2 extract was concentrated under reduced pressure.