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Reactivity of 1-arylnitrosoethylenes towards indole derivatives

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Abstract

The reactivity of 1-arylnitrosoalkenes toward indole, 1-methylindole, and 3-methylindole is described. In contrast with the previously observed chemical behaviour of 1-(p-bromophenyl)nitrosoethylene towards pyrrole, the studied heterodienes reacted with indole and 1-methylindole to afford E-oximes via hetero-Diels–Alder reactions. The reaction with 3-methylindole also proceeds via cycloaddition giving the corresponding 1,2-oxazine. Quantum chemical calculations, at the DFT level, indicate that the energy barriers associated with the reactions between 1-(p-bromophenyl)nitrosoethylene and indole and its derivatives are similar to those observed for the reaction between this nitrosoalkene and pyrrole. However, the calculated energy of the theoretical Diels–Alder cycloadducts involving indole and pyrrole clearly suggests that the Diels–Alder reaction is privileged in the case of indole. Furthermore, in the case of the indole, the energy difference between reactants and products clearly favors the regiochemistry observed experimentally.

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Acknowledgments

Thanks are due to Coimbra Chemistry Centre (CQC), supported by the Portuguese Agency for Scientific Research, “Fundação para a Ciência e a Tecnologia” (FCT), through Project No. 007630 UID/QUI/00313/2013, co-funded by COMPETE2020-UE. Sandra C. C. Nunes and Susana M. M. Lopes also acknowledge FCT for postdoctoral research grants SFRH/BPD/71683/2010, SFRH/BPD/84413/2012, respectively. We acknowledge the UC-NMR facility for obtaining the NMR data (http://www.nmrccc.uc.pt).

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Authors and Affiliations

  1. CQC and Department of Chemistry, University of Coimbra, 3004-535, Coimbra, Portugal

    Susana M. M. Lopes, Sandra C. C. Nunes, Cátia C. Caratão, Alberto A. C. C. Pais & Teresa M. V. D. Pinho e Melo

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  1. Susana M. M. Lopes
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  2. Sandra C. C. Nunes
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  3. Cátia C. Caratão
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  4. Alberto A. C. C. Pais
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  5. Teresa M. V. D. Pinho e Melo
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Corresponding author

Correspondence to Teresa M. V. D. Pinho e Melo.

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Lopes, S.M.M., Nunes, S.C.C., Caratão, C.C. et al. Reactivity of 1-arylnitrosoethylenes towards indole derivatives. Monatsh Chem 147, 1565–1573 (2016). https://doi.org/10.1007/s00706-016-1763-1

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  • DOI: https://doi.org/10.1007/s00706-016-1763-1

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