Covalently Anchored Sulfonic Acid on Silica Gel as an Efficient and Reusable Heterogeneous Catalyst for the One-Pot Synthesis of Hantzsch 1,4-Dihydropyridines under Solvent-Free Conditions

Abstract

A highly efficient one-pot synthesis of Hantzsch 1,4-dihydropyridines under solvent-free conditions catalyzed by sulfonic acid covalently anchored onto the surface of silica gel is reported here. All types of aldehydes, including aromatic, unsaturated, and heterocyclic aldehydes, gave excellent yields. The silica gel/sulfonic acid catalyst (SiO₂-SO₃H) is completely heterogeneous and can be recycled for eight consecutive runs without significant loss of activity.

Key words

1,3-dicarbonyl compounds - supported catalysis - 1,4-dihydropyridines - heterogeneous catalysis - solvent-free conditions

References

• 1a Hantzsch A. Ber. Dtsch. Chem. Ges.  1881,  14:  1637 
• 1b Hantzsch A. Justus Liebigs Ann. Chem.  1882,  215:  1 
• 2 Mauzeral D. Westheimer FH. J. Am. Chem. Soc.  1955,  77:  2261 
• 3 Flaim SF. Zelis R. Fed. Proc.  1981,  40:  2877 
• 4 Klusa V. Drugs Future  1995,  20:  135 
• 5 Bretzel RG. Bollen CC. Maeser E. Federlin KF. Drugs Future  1992,  17:  465 
• 6 Boer R. Gekeler V. Drugs Future  1995,  20:  499 
• 7a Maheswara M. Siddaiah V. Rao YK. Tzeng Y.-M. Sridhar C. J. Mol. Catal. A: Chem.  2006,  260:  179 ; and references cited therein
• 7b Sharma GVM. Reddy KL. Lakshmi K. Radha Krishna P. Synthesis  2006,  55 ; and references cited therein
• 8a Yin L. Liebscher J. Chem. Rev.  2007,  107:  133 
• 8b Paul S. Clark JH. J. Mol. Catal. A: Chem.  2004,  215:  107 
• 8c Choudhary D. Paul S. Gupta R. Clark JH. Green Chem.  2006,  9:  431 
• 9a Das B. Venkateswarlu K. Holla H. Krishnaiah M. J. Mol. Catal. A: Chem.  2006,  253:  107 
• 9b Karimi B. Khalkhali M. J. Mol. Catal. A: Chem.  2005,  232:  113 
• 9c Shylesh S. Sharma S. Mirajkar SP. Singh AP. J. Mol. Catal. A: Chem.  2004,  212:  219 
• 9d Wilson K. Lee AF. Macquarrie DJ. Clark JH. Appl. Catal., A  2002,  228:  127 
• 9e Das D. Lee J.-F. Cheng S. Chem. Commun.  2001,  2178 
• 9f Van Rhijn WM. De Vos DE. Sels BF. Bossaert WD. Jacobs PA. Chem. Commun.  1998,  317 
• 9g Gupta R. Paul S. Gupta R. J. Mol. Catal. A: Chem.  2007,  266:  50 
• 10 Manabe K. Kobayashi S. Adv. Synth. Catal.  2002,  344:  270 
• 11 Wang X. Quan Z. Wang F. Wang M. Zhang Z. Li Z. Synth. Commun.  2006,  36:  451 
• 12a Zhang C. Liao L. Gong S. Green Chem.  2007,  9:  303 
• 12b de la Hoz A. Díaz-Ortiz A. Moreno A. Chem. Soc. Rev.  2005,  34:  164 
• 12c Loupy A. Microwaves in Organic Synthesis   Wiley-VCH; Weinheim: 2002.