Yttria-Zirconia–Based Lewis Acid Catalysis of the Biginelli Reaction: An Efficient One-Pot Synthesis of 3,4-Dihydropyrimidin-2-(1H)-ones

REFERENCES

• Mizuno , N. ; Misono , M. Heterogeneous catalysis . Chem. Rev. 1998 , 98 , 199 – 218 .
   PubMed Web of Science ®Google Scholar
• (a) Kappe , C. O. One hundred years of the Biginelli dihydropyrimidine synthesis . Tetrahedron 1993 , 49 , 6937 – 6963 . (b) Kappe , C. O. ; Kumar , D. ; Varma , R. S. Microwave-assisted high speed parallel synthesis of 4-aryl-3,4-dihydropyrimidin-2-(1H)-ones using a solvent-less Biginelli condensation protocol . Synthesis 1999 , 1799 – 1803 , and the references therein .
   Web of Science ®Google Scholar
• (a) Atwal , K. S. ; Rovnyak , G. C. ; O'Reilly , B. C. ; Schwartz , J. Substituted 1,4-dihydropyrimidines: Synthesis of selectively functionalized 2-hetero-1,4-dihydropyrimidines. J. Org. Chem. 1989, 54, 5898–5907; (b) Atwal , K. S. ; Rovnyak , G. C. ; Kimball , S. D. ; Floyd , D. M. ; Moreland , S. ; Swanson , B. N. ; Gougoutas , J. Z. ; Schwartz , J. ; Smillie , K. M. ; Malley , M. F. Dihydropyrimidine calcium channel blockers II: 3-Substituted-4-aryl-1,4-dihydro-6-methyl-5-pyrimidinecarboxylic acid esters as potent mimics of dihydropyrimidines. J. Med. Chem. 1990, 33, 2629–2635; (c) Atwal , K. S. ; Swanson , B. N. ; Unger , S. E. ; Floyd , D. M. ; Moreland , S. ; Hedberg , A. ; O'Reilly , B. C. Dihydropyrimidine calcium channel blockers 3: 3-Carbamoyl-4-aryl-1,2,3,4-tetrahydro-6-methyl-5-pyrimidinecarboxylic acid esters as orally effective antihypertensive agents. J. Med. Chem. 1991, 34, 806–811; (d) Rovnyak , G. C. ; Atwal , K. S. ; Hedgberg , A. ; Kimball , S. D. ; Moreland S. ; Gougoutas , J. Z. ; O' Reilly , B. C. ; Schwartz , J. ; Malley , M. F. Dihydropyrimidine calcium channel blockers 4: Basic 3-substituted-4-aryl-1,4-dihydropyrimidine-5-carboxylic acid esters: Potent antihypertensive agents. J. Med. Chem. 1992, 35, 3254–3263, and the references therein; (e) Rovnyak , G. C. ; Kimball , S. D. ; Beyer , B. ; Cucinotta , G. ; DiMarco , J. D. ; Gougoutas , J. ; Hedberg , A. ; Malley , M. ; McCarthy , J. P. ; Moreland , S. Calcium entry blockers and activators: Conformational and structural determinants of dihydropyrimidine calcium channel modulators. J. Med. Chem. 1995, 38, 119–129; (f) Kappe , C. O. ; Fabian , W. M. F. Conformational analysis of 4-aryl-dihydropyrimidine calcium channel modulators: A comparison of ab initio, semiempirical, and x-ray crystallographic studies. Tetrahedron 1997, 53, 2803–2816.
   Web of Science ®Google Scholar
• (a) Patil , A. D. ; Kumar , N. N. ; Kokke , W. C. ; Bean , M. F. ; Freyer , A. J. ; DeBrosse , C. ; Mai , S. ; Truneh , A. ; Faulkner , D. J. Novel alkaloids from the sponge Batzella sp.: Inhibitors of HIV gp120-Human CD4 binding . J. Org. Chem. 1995 , 60 , 1182 – 1188 ; (b) Snider , B. B. ; Chen , J. ; Patil , A. D. ; Freyer , A. Synthesis of the tricyclic portions of batzelladines A, B, and D: Revision of the stereochemistry of batzelladines A and D . Tetrahedron Lett. 1996 , 37 , 6977 – 6980 .
   Web of Science ®Google Scholar
• Biginelli , P. Acid-catalyzed cyclocondensation reaction of ethyl acetoacetate, benzaldehyde, urea . Gazz. Chim. Ital. 1893 , 23 , 360 – 416 .
   Google Scholar
• (a) Barluenga , J. ; Tomás , M. ; Ballesteros , M. ; López , L. A. 1,4-Cycloaddition of 1,3-diazabutadiene with enamines: An efficient route to the pyrimidine ring . Tetrahedron Lett. 1989 , 30 , 4573 – 4576 ; (b) O'Reilly , B. C. ; Atwal , K. S. Synthesis of substituted 1,2,3,4-tetrahydro-6-methyl-2-oxo-5-pyrimidine carboxylic acid esters: The Biginelli condensation revisited . Heterocycles 1987 , 26 , 1185 – 1188 ; (c) O'Reilly , B. C. ; Atwal , K. S. ; Gougoutas , J. Z. ; Malley , M. F. Synthesis of substituted 1,2,3,4-tetrahydro-6-methyl-2-thioxo-5-pyrimidine carboxylic acid esters . Heterocycles 1987 , 26 , 1189 – 1192 .
   Web of Science ®Google Scholar
• (a) Hu , E. H. ; Sidler , D. R. ; Dolling , U.-H. Unprecedented catalytic three-component one-pot condensation reaction: An efficient synthesis of 5-alkoxycarbonyl-4-aryl-3,4-dihydropyrimidin-2(1H)-ones . J. Org. Chem. 1998 , 63 , 3454 – 3457 ; (b) Lu , J. ; Ma , H. Iron(III)-catalyzed synthesis of dihydropyrimidinones: Improved conditions for the Biginelli reaction . Synlett 2000 , 63 – 64 ; (c) Lu , J. ; Bai , Y. ; Wang , Z. ; Yang , B. ; Ma , H. One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using lanthanum chloride as a catalyst . Tetrahedron Lett. 2000 , 41 , 9075 – 9078 ; (d) Ma , Y. ; Qian , C. ; Wang , L. ; Yang , M. Lanthanide triflate catalyzed Biginelli reaction one-pot synthesis of dihydropyrimidinones under solvent-less conditions . J. Org. Chem. 2000 , 65 , 3864 – 3868 ; (e) Kappe , C. O. ; Falsone , S. F. Polyphosphate ester-mediated synthesis of dihydropyrimidines: Improved condition for the Biginelli reaction . Synlett 1998 , 718 – 720 ; (f) Ranu , B. C. ; Hajra , A. ; Jana , U. Indium(III) chloride-catalyzed one-pot synthesis of dihydropyrimidinones by a three-component coupling of 1,3-dicarbonyl compounds, aldehydes, and urea: An improved procedure for the Biginelli reaction . J. Org. Chem. 2000 , 65 , 6270 – 6272 ; (g) Fu , N.-Y. ; Yuan , Y.-F. ; Cao , Z. ; Wang , S.-W. ; Wang , J.-T. ; Peppe , C. Indium(III) bromide-catalyzed preparation of dihydropyrimidine: Improved protocol conditions for the Biginelli reaction . Tetrahedron 2002 , 58 , 4801 – 4807 ; (h) Yadav , J. S. ; Subba Reddy , B. V. ; Srinivas , R. ; Venugopal , C. ; Ramalingam , T. LiClO4-catalyzed one-pot synthesis of dihydropyrimidinones: An improved protocol for Biginelli reaction . Synthesis 2001 , 1341 – 1345 ; (i) Lu , J. ; Bai , Y. Catalysis of the Biginelli reaction by ferric and nickel chloride hexahydrate: One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones . Synthesis 2002 , 466 ; (j) Reddy , C. V. ; Mahesh , M. ; Raju , P. V. K. ; Babu , R. ; Reddy , V. V. N. Zirconium(IV) chloride catalyzed one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones . Tetrahedron Lett. 2002 , 43 , 2657 – 2659 ; (k) Kumar , K. A. ; Kasthuraiah , M. ; Reddy , C. S. ; Reddy , C. D. Mn(OAc)3.2H2O-mediated, three-component, one-pot condensation reaction: An efficient synthesis of 4-aryl substituted 3,4-dihydropyrimidin-2-ones . Tetrahedron Lett. 2001 , 42 , 7873 – 7875 .
   Web of Science ®Google Scholar
• (a) Rani , V. R. ; Srinivas , N. ; Kishan , M. R. ; Kulkarni , S. J. ; Ragavan , K. V. Zeolite- catalyzed cyclocondensation reaction for the selective synthesis of 3,4-dihydropyrimidin-2-ones. Green Chem. 2001, 42, 305–306; (b) Peng , J. ; Deng , Y. Ionic liquids catalyzed Biginelli reaction under solvent-free conditions. Tetrahedron Lett. 2001, 42, 5917–5919; (c) Yadav , J. S. ; Subba Reddy , B. V. ; Jagan Reddy , E. ; Ramalingam , T. Microwave-assisted efficient synthesis of dihydropyrimidine: Improved high yielding protocol for the Biginelli reaction. J. Chem. Res., Synop. 2000, 354–355; (d) Gupta , R. ; Gupta , A. K. ; Paul , S. ; Kachroo , P. L. Improved syntheses of some ethyl 4-aryl-6-methyl-1,2,3,4-tetrahydropyrimidin-2-one/thione-5-carboxylate by microwave irradiation. Indian J. Chem. 1995, 34B, 151–152; (e) Yadav , J. S. ; Reddy , B. V. S. ; Reddy , K. B. ; Raj , K. S. ; Prasad , A. R. Ultrasound-accelerated synthesis of 3,4-dihydropyrimidin-2(1H)-ones with ceric ammonium nitrate. J. Chem. Soc. Perkin, Trans. 2001, 1, 1939–1941; (f) Bigi , F. ; Carloni , S. ; Frullanti , B. ; Maggi , R. ; Sartori , G. P. A revision of the Biginelli reaction under solid acid catalysis: Solvent-free synthesis of dihydropyrimidines over montmorillonite KSF. Tetrahedron Lett. 1999, 40, 3465–3468.
   Google Scholar
• (a) Shaabani , A. ; Bazgir , A. ; Teimouri , F. Ammonium chloride-catalyzed one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones under solvent-free conditions . Tetrahedran Lett. 2003 , 44 , 857 – 859 ; (b) Rosi Reddy , K. ; Venkateshwar Reddy , C. ; Mahesh , M. ; Raju , P. V. K. ; Narayana Reddy , V. V. New environmentally friendly solvent-free synthesis of dihydropyrimidinones catalyzed by N-butyl-N, N-dimethyl-α-phenylethylammonium bromide . Tetrahedron Lett. 2003 , 44 , 8173 – 8175 ; (c) Tu , S. ; Fang , F. ; Miao , C. ; Jiang , H. ; Feng , Y. ; Shi , D. ; Wanf , X. One-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones using boric acid as catalyst . Tetrahedron Lett. 2003 , 44 , 6153 – 6155 ; (d) (i) Varala , M. R. ; Alam , M. ; Adapa , S. R. Bismuthtriflates–catalyzed one-pot synthesis of 3,4-dihydropyrimidin-2-(1H)-ones: An improved protocol for the Biginelli reaction . Synlett 2003 , 67 – 70 ; (ii) Paraskar , A. S. ; Dewkar , G. K. ; Sudalai , A. Cu(OTf)2: A reusable catalyst for high-yield synthesis of 3,4-dihydropyrimidin-2(1H)-ones . Tetrahedron Lett. 2003 , 44 , 3305 – 3308 ; (e) (i) Narasaiah , V. A. ; Basak , A. K. ; Nagaiah , K. Cadmium chloride: An efficient catalyst for one-pot synthesis of 3,4-dihydropyrimidin-2(1H)-ones . Synthesis 2004 , 8 , 1253 – 1256 ; (ii) Sun , Q. ; Wang , Y.-Q. ; Ge , Z-M. ; Cheng , T.-M. ; Li , R.-T. A highly efficient solvent-free synthesis of dihydropyrimidinones catalyzed by zinc chloride . Synthesis 2004 , 7 , 1047 – 1050 ; (f) Sabitha , G. ; Reddy , G. S. K. K. ; Reddy , C. S. ; Yadav , J. S. One-pot synthesis of dihydropyrimidinones using iodotrimethylsilane: Facile and new improved protocol for the Biginelli reaction at room temperature . Synlett 2003 , 858 – 860 ; (g) Yadav , J. S. ; Reddy , B. V. S. ; Sridhar , P. ; Reddy , J. S. S. ; Nagaiah , K. ; Ligaiah , N. ; Saiprasad , P. S. Green protocol for the Biginelli three-component reaction: Ag3PW12O20 as a novel-tolerant heteropolyacid for the synthesis of 3,4-dihydropyrimidinones . Eur. J. Org. Chem. 2004 , 552 – 557 . (h) Gangadasu , B. ; Palaniappan , S. ; Rao , J. V. One-pot synthesis of dihydropyrimidinones using polyaniline-bismoclite complexes: A facile and reusuable catalyst for the Biginelli reaction . Synlett 2004 , 1285 – 1287 .
   Web of Science ®Google Scholar
• (a) Keshava Raja , A. ; Hegde , V. R. ; Pandey , B. ; Ramaswamy , A. V. ; Kumar , P. ; Ravindranathan , T. A yttrium-based strong Lewis acid for the heterogeneous catalysis of the Diels–Alder reaction. Angew. Chem., Int. Ed. Engl. 1995, 34, 2143–2145; (b) Kumar , P. ; Pandey , R. K. ; Bodas , M. S. ; Dagade , S. P. ; Dongare , M. K. ; Ramaswamy , A. V. Acylation of alcohols, thiols, and amines with carboxylic acid catalyzed by yttria-zirconia-based Lewis acid. J. Mol. Catal. A 2002, 181, 207–213.
   Google Scholar
• Furniss , B. S. ; Hannaford , A. J. ; Rogeres , V. ; Smith , P. W. G. ; Tatchell , A. R. (Eds.). Vogel's Textbook of Practical Organic Chemistry. , 4th ed. ; ELBS/Longman : London , 1978 .
   Google Scholar