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

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

References

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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: [phone], E-mail: [e-mail]].

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.