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Switching diastereoselectivity of direct Mannich-type reaction of cyclic ketones by polymeric laponite nanoclay catalyst

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Abstract

A new polymeric laponite nanoclay heterogeneous catalytic system based on HPMC (hydroxypropyl methyl cellulose) was developed for direct Mannich-type reaction of ketones with substituted benzaldehydes and anilines to afford corresponding β-amino ketones in good to high yields. Interestingly, cyclic ketones exhibited different chemoselectivity. Cyclopentanone underwent aldol condensation to give crossed-aldol product, while cyclohexanone and cyclopentanone afforded corresponding Mannich adducts. In the case of cyclohexanone, stereoselectivity was changed depending on the nature of the substitution on benzaldehydes, in which, moderate electron-donating and electron-withdrawing groups afforded the anti isomer as major products, but strongly electron-donating substituted benzaldehydes led to syn isomer as the major Mannich adducts. Mannich reaction with cycloheptanone led to Mannich adducts with excellent syn selectivity.

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Acknowledgments

The Research Council of the University of Maragheh is acknowledged for financial support.

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Authors and Affiliations

  1. Department of Chemistry, University of Maragheh, P. O. Box 55181-83111, Maragheh, Iran

    Bagher Eftekhari-Sis, Sahar Mohajer & Gholam Reza Mahdavinia

  2. Department of Chemistry, Payame Noor University, P. O. Box 19395-3697, Tehran, Iran

    Maryam Zirak

  3. Department of Physics, Ondokuz Mayis University, TR-55139, Samsun, Turkey

    Orhan Büyükgüngör

Authors
  1. Bagher Eftekhari-Sis
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  2. Sahar Mohajer
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  5. Orhan Büyükgüngör
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Correspondence to Bagher Eftekhari-Sis.

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Eftekhari-Sis, B., Mohajer, S., Zirak, M. et al. Switching diastereoselectivity of direct Mannich-type reaction of cyclic ketones by polymeric laponite nanoclay catalyst. J IRAN CHEM SOC 13, 609–615 (2016). https://doi.org/10.1007/s13738-015-0772-z

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