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The reaction of 2-amino-4\(H\)-pyrans with \(N\)-bromosuccinimide

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Abstract

The reaction of racemic 2-amino-4\(H\)-pyrans, such as 3-amino-1-aryl-1\(H\)-benzo\([f]\)chromene-2-carbonitriles, with \(N\)-bromosuccinimide (NBS), in \(\hbox {CH}_{2}\hbox {Cl}_{2}\), at room temperature, is a very quick, regio, stereoselective, and high yielding process, affording major racemic \((1S,2S)\)-2-bromo-3-imino-benzo\([f]\)chromene or racemic \((1S,2S)\)-2-bromo-3-(bromoimino)-benzo\([f]\)chromene derivatives, when using 1.0 or 2.2 equivalents of NBS, respectively. This reaction, extended to isomeric 2-amino-4-aryl-4\(H\)-benzo\([h]\)chromene-3-carbonitriles, showed an unexpected reactivity, affording racemic (3\(S\),4\(S)\)-3-bromo-2-(bromoimino)-benzo\([h]\)chromene-3-carbonitriles or 2-oxo-2\(H\)-benzo\([h]\)chromene-3-carbonitriles, when using 2.2 or 1.0 equivalents of NBS, respectively. The reaction of alkyl 6-amino-5-cyano-2-methyl-4\(H\)-pyran-3-carboxylates has yielded unstable racemic (3\(S\),4\(S)\)-alkyl 3-bromo-2-(bromoimino)-3-cyano-6-methyl-3,4-dihydro-2\(H\)-pyran-5-carboxylates. The mechanism of these reactions has been investigated by computational methods.

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Notes

  1. We thank one of the reviewers for suggesting us to carry out this experiment.

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Acknowledgments

JMC thanks MINECO for Grant SAF2012-33304, W. Malicka for the preparation of some starting materials. Daniel da Silva thanks EU (COST Action) for support. LI thanks Comunidad de Madrid (BIPEDD-2: S2010-BMD-2457). ES thanks MINECO for grant CTQ2009-10478 and CESGA for generous allocation of computing resources.

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Authors and Affiliations

  1. Laboratorio de Química Médica, IQOG (CSIC), Juan de la Cierva, 3, 28006, Madrid, Spain

    Abdelouahid Samadi, Daniel Silva, Mourad Chioua & José Marco-Contelles

  2. SEPCO (IQOG, CSIC), Juan de la Cierva, 3, 28006, Madrid, Spain

    Elena Soriano

  3. Instituto de Química-Física “Rocasolano” (CSIC), Serrano, 119, 28006, Madrid, Spain

    Lourdes Infantes

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  1. Abdelouahid Samadi
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Correspondence to Elena Soriano.

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Samadi, A., Silva, D., Chioua, M. et al. The reaction of 2-amino-4\(H\)-pyrans with \(N\)-bromosuccinimide. Mol Divers 19, 103–122 (2015). https://doi.org/10.1007/s11030-014-9560-4

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