Amine-functionalized Metal-Organic Frameworks: An Efficient and Recyclable Heterogeneous Catalyst for the Knoevenagel Condensation Reaction

Abstract

A highly efficient and reusable catalyst based on metal-organic frameworks (MOF) has been synthesized by post-functionalization and applied in Knoevenagel condensations of various aldehydes and ketones. The catalytic efficiency was demonstrated by the high conversion (over 85−98%) of the reactants under mild conditions. The catalyst maintained its unique framework after the reaction and could be recycled and reused several times without significant loss of activity.

Key words

Knoevenagel condensation - metal-organic frameworks - heterogeneous catalysis - carbon–carbon bond - aldehyde - ketone

• References and Notes

• 1 Knoevenagel E. Ber. Dtsch. Chem. Ges. 1894; 27: 2345
• 2a Knoevenagel E. Ber. Dtsch. Chem. Ges. 1898; 31: 2585
• 2b Jones G. Org. React. (N. Y.) 1967; 15: 204
• 2c Tietze LF, Beifuss U In Comprehensive Organic Synthesis . Vol 2. Trost BM. Pergamon Press; Oxford: 1991: 341
• 3 Solomons TW. G, Fryhle C. Organic Chemistry . Wiley; New York: 2009
• 4a Rao PS, Venkataratnam RV. Tetrahedron Lett. 1991; 32: 5821
• 4b Prajapati D, Sandhu JS. J. Chem. Soc., Perkin Trans. 1 1993; 739
• 4c Lehnert W. Tetrahedron Lett. 1970; 11: 4723
• 4d Dai G, Shi D, Zhou L, Huaxue Y. Chin. J. Appl. Chem. 1995; 12: 104
• 4e Gill C, Pandhare G, Raut R, Gore V, Gholap S. Bull. Catal. Soc. India 2008; 7: 153
• 5a Mogilaiah K, Reddy CS. Synth. Commun. 2003; 33: 3131
• 5b Mallouk S, Bougrin K, Laghzizil A, Benhida R. Molecules 2010; 15: 813
• 5c Bhuiyan MM. H, Hossain MI, Ashraful M, Mahmud MM. J. Chem. 2012; 2: 30
• 6a McNulty J, Steere JA, Wolf S. Tetrahedron Lett. 1998; 39: 8013
• 6b Palmisano G, Tibiletti F, Penoni A, Colombo F, Tollari S, Garella D, Tagliapietra S, Cravotto G. Ultrason. Sonochem. 2011; 18: 652
• 7a Pratap UR, Jawale DV, Waghmare RA, Lingampalle DL, Mane RA. New J. Chem. 2011; 35: 49
• 7b Wang C, Guan Z, He Y. Green Chem. 2011; 13: 2048
• 8a Xia Y, Yang Z.-Y, Brossi A, Lee K.-H. Org. Lett. 1999; 1: 2113
• 8b Guo G, Arvanitis EA, Pottorf RS, Player MP. J. Comb. Chem. 2003; 5: 408
• 9a Ying A.-G, Liu L, Wu G.-F, Chen X.-Z, Ye W.-D, Chen J.-H, Zhang K.-Y. Chem. Res. Chin. Univ. 2009; 25: 876
• 9b Khan FA, Dash FJ, Satapathy R, Upadhyay SK. Tetrahedron Lett. 2004; 45: 3055
• 9c Verdia P, Santamarta F, Tojo E. Molecules 2011; 16: 4379
• 10a Bigi F, Conforti ML, Maggi R, Piccinno A, Sartori G. Green Chem. 2000; 2: 101
• 10b Wang S, Ren Z, Cao W, Tong W. Synth. Commun. 2001; 31: 673
• 10c Oskooie HA, Heravi MM, Derikvand F, Khorasani M, Bamoharram FF. Synth. Commun. 2006; 36: 2819
• 11a Pasha MA, Manjula K. J. Saudi Chem. Soc. 2011; 15: 283
• 11b Rong L, Li X, Wang H, Shi D, Tu S, Zhuang Q. Synth. Commun. 2006; 36: 2407
• 11c Ren Z, Cao W, Tong W. Synth. Commun. 2002; 32: 3475
• 12a Dimitratos N, Lopez-Sanchez JA, Hutchings G. J. Chem. Sci. 2012; 3: 20
• 12b Anastas PT, Kirchhoff MM, Williamson TC. Appl. Catal. A. 2001; 221: 3
• 13a Kitagawa S, Kitaura R, Noro S. Angew. Chem. Int. Ed. 2004; 43: 2334
• 13b Dhakshinamoorthy A, Alvaro M, Garcia H. Chem. Commun. 2012; 48: 11275
• 14 Custelcean R, Gorbunova MG. J. Am. Chem. Soc. 2005; 127: 16362
• 15 Kitaura R, Onoyama G, Sakamoto H, Matsuda R, Noro S, Kitagawa S. Angew. Chem. Int. Ed. 2004; 43: 2684
• 16 Goto YH, Shinkai SS, Sada K. J. Am. Chem. Soc. 2008; 130: 14354
• 17 Nagata S, Sato H, Sugikawa K, Kokado K, Sada K. CrystEngComm 2012; 14: 4137
• 18 Haensch C, Hoeppener S, Schubert US. Nanotechnology 2008; 19: 035703
• 19 Adenier A, Chehimi MM, Gallardo I, Pinson J, Vila N. Langmuir 2004; 20: 8243
• 20 Freeman F. Chem. Rev. 1980; 80: 329
• 21 Macquarrie DJ, Jackson DB, Clark JH In Supported catalysts and their application . Sherrington DC, Kybett AP. RSC; Cambridge: 2001
• 22 Gupta R, Gupta M, Paul S, Gupta R. Bull. Korean Chem. Soc. 2009; 30: 2419
• 23 Pal R. Int. J. Adv. Chem. 2014; 2: 27
• 24 Knoevenagel Condensations Using MOF-NH₂; General Procedure Catalyst corresponding to 0.13 mmol –NH₂ groups (based on the total amount of amino groups in the catalytic material) was added to a solution of malononitrile or ethyl cyanoacetate (1 mmol) and aldehyde or ketone (1 mmol) in DMF (6 mL) at 80 °C under a nitrogen atmosphere. After the reaction was complete, the yield was monitored by GC analysis.
• 25 Xamena FX. L, Cirujano FG, Corma A. Microporous Mesoporous Mater. 2012; 157: 112