Magnetically Separable Cu-Carboxylate MOF Catalyst for the Henry Reaction

Abstract

An air-stable Cu-carboxylate MOF complex can catalyze the cross-coupling reaction of phenylacetylene with 2-oxazolidone and Henry reaction. The Cu-carboxylate MOF encapsulated magnetic beads (MOF-MB II) was also prepared. The MOF-MB II was successfully reused in the Henry reaction by a simple magnetic separation.

Key words

catalyst - metal-organic framework - magnetic separation - reuse

• References and Notes


For reviews on sustainable catalysis, see:
• 1a Handbook of Asymmetric Heterogeneous Catalysis . Ding K, Uozumi Y. Wiley-VCH; Weinheim: 2008
• 1b Catalyst Separation Recovery and Recycling: Chemistry and Process Design. Cole-Hamilton DJ, Tooze RP. Springer; Berlin: 2006
• 1c Fraile JM, Garcìa JI, Mayoral JA. Chem. Rev. 2009; 109: 360
• 1d Fraile JM, Garcìa JI, Mayoral JA. Coord. Chem. Rev. 2008; 252: 624
• 1e Schätz A, Reiser O, Stark W. Chem. Eur. J. 2010; 16: 8950
• 2 A review of the magnetic separation of catalysts: Polshettiwar V, Luque R, Fihri A, Zhu H, Bouhrara M, Basset J.-M. Chem. Rev. 2011; 111: 3036

Selected examples of magnetic separation of catalysts:
• 3a Yoon T.-J, Lee W, Oh Y.-S, Lee J.-K. New J. Chem. 2003; 27: 227
• 3b Lu A.-H, Schmidt W, Matoussevitch N, Bönnemann H, Spliethoff B, Tesche B, Bill E, Kiefer W, Schüth F. Angew. Chem. Int. Ed. 2004; 43: 4303
• 3c Tsang SC, Caps V, Paraskevas I, Chadwick D, Thompsett D. Angew. Chem. Int. Ed. 2004; 43: 5645
• 3d Stevens PD, Fan J, Gardimalla HM. R, Yen M, Gao Y. Org. Lett. 2005; 7: 2085
• 3e Hu AG, Yee T, Lin W. J. Am. Chem. Soc. 2005; 127: 12486
• 3f Jun C.-H, Park YJ, Yeon Y.-R, Choi J.-R, Lee W.-R, Ko S.-J, Cheon J. Chem. Commun. 2006; 1619
• 3g Phan NT. S, Gill CS, Nguyen JV, Zhang ZJ, Jones CW. Angew. Chem. Int. Ed. 2006; 45: 2209
• 3h Kim J, Lee JE, Lee J, Jang Y, Kim S.-W, An K, Yu JH, Hyeon T. Angew. Chem. Int. Ed. 2006; 45: 4789
• 3i Abu-Reziq R, Alper H, Wang D, Post ML. J. Am. Chem. Soc. 2006; 128: 5279
• 3j Ko S, Jang J. Angew. Chem. Int. Ed. 2006; 45: 7564
• 3k Guin D, Baruwati B, Manorama SV. Org. Lett. 2007; 9: 1419
• 3l Yoon H, Ko S, Jang J. Chem. Commun. 2007; 1468
• 3m Lin P.-C, Ueng S.-H, Yu S.-C, Jan M.-D, Adak AK, Yu C.-C, Lin C.-C. Org. Lett. 2007; 9: 2131
• 3n Kawamura M, Sato K. Chem. Commun. 2007; 3404
• 3o Kwon MS, Park IS, Jang JS, Lee JS, Park J. Org. Lett. 2007; 9: 3417
• 3p Dálaigh CÓ, Corr SA, Gun’ko YS, Connon J. Angew. Chem. Int. Ed. 2007; 46: 4329
• 3q Shokouhimehr M, Piao Y, Kim J, Jang Y, Hyeon T. Angew. Chem. Int. Ed. 2007; 46: 7039
• 3r Liu J, Peng X, Sun W, Zhao Y, Xia C. Org. Lett. 2008; 10: 3933
• 3s Hirakawa T, Tanaka S, Usuki N, Kanzaki H, Kishimoto M, Kitamura M. Eur. J. Org. Chem. 2009; 6: 789
• 3t Zhu Y, Loo K, Ng H, Li C, Stubbs LP, Siong CF, Tan M, Peng SC. Adv. Synth. Catal. 2009; 351: 2650
• 3u Yan J.-M, Zhang X.-B, Akita T, Haruta M, Xu Q. J. Am. Chem. Soc. 2010; 132: 5326
• 3v Shylesh S, Schuenemann V, Thiel WR. Angew. Chem. Int. Ed. 2010; 49: 3428
• 3w Deng Y, Cai Y, Sun Z, Liu C, Wei J, Li W, Liu C, Wang Y, Zhao D. J. Am. Chem. Soc. 2010; 132: 8466
• 3x Wang BG, Ma BC, Wang Q, Wang W. Adv. Synth. Catal. 2010; 352: 2923
• 3y Ranganath KV. S, Kloesges J, Schäfer AH, Glorius F. Angew. Chem. Int. Ed. 2010; 49: 7786
• 3z Wu L, He Y.-M, Fan Q.-H. Adv. Synth. Catal. 2011; 353: 2915

Reviews of MOF:
• 4a Kitagawa S, Kitaura R, Noro S.-i. Angew. Chem. Int. Ed. 2004; 43: 2334
• 4b Long J, Yaghi OM. Chem. Soc. Rev. 2009; 38: 1213

Selected examples of MOF as catalysts:
• 5a Seo JS, Whang D, Lee H, Jun SI, Oh J, Jeon YJ, Kim K. Nature (London) 2000; 404: 982
• 5b Takizawa S, Somei H, Jayaprakash D, Sasai H. Angew. Chem. Int. Ed. 2003; 42: 5711
• 5c Evans OR, Ngo HL, Lin W. J. Am. Chem. Soc. 2001; 123: 10395
• 5d Hu A, Ngo HL, Lin W. Angew. Chem. Int. Ed. 2003; 42: 6000
• 5e Hu A, Ngo HL, Lin W. J. Am. Chem. Soc. 2003; 125: 11490
• 5f Wang X, Ding K. J. Am. Chem. Soc. 2004; 126: 10524
• 5g Wang X, Wang X, Guo H, Wang Z, Ding K. Chem.–Eur. J. 2005; 11: 4078
• 5h Wang X, Shi L, Li M, Ding K. Angew. Chem. Int. Ed. 2005; 44: 6362
• 5i Liang Y, Jing Q, Li X, Shi L, Ding K. J. Am. Chem. Soc. 2005; 127: 7694
• 5j Cotton FA, Murillo CA, Stiriba SE, Wang X, Yu R. Inorg. Chem. 2005; 44: 8223
• 5k Peng HY, Lam CK. T, Mak CW, Cai Z, Ma WT, Li YX, Wong HN. C. J. Am. Chem. Soc. 2005; 127: 9603
• 5l Harada T, Nakatsugawa M. Synlett 2006; 321
• 5m Dybtsev DN, Nuzhdin AL, Chun H, Bryliakov KP, Talsi EP, Fedin VP, Kim K. Angew. Chem. Int. Ed. 2006; 45: 916
• 5n Liang Y, Wang Z, Ding K. Adv. Synth. Catal. 2006; 348: 1533
• 5o Cho SH, Ma BS, Nguyen T, Hupp JT, Albrecht-Schmitt TE. Chem. Commun. 2006; 2563
• 5p Shi L, Wang X, Sandoval CA, Li M, Qi Q, Li Z, Ding K. Angew. Chem. Int. Ed. 2006; 45: 4108
• 5q Cho SH, Gadzikwa T, Afshari M, Nguyen ST, Hupp JT. Eur. J. Inorg. Chem. 2007; 4863
• 5r Nuzhdin AL, Dybtsev DN, Bryliakov KP, Talsi EP, Fedin VP. J. Am. Chem. Soc. 2007; 129: 12958
• 5s Wu CD, Hu A, Zhang L, Lin W. J. Am. Chem. Soc. 2005; 127: 8940
• 5t Wu CD, Lin W. Angew. Chem. Int. Ed. 2007; 46: 1075
• 5u Tanaka K, Oda S, Shiro M. Chem. Commun. 2008; 820
• 5v Ingleson MJ, Barrio JP, Bacsa J, Dickinson C, Park H, Rosseinsky MJ. Chem. Commun. 2008; 1287
• 5w Garcia JI, Lopez-Sanchez B, Mayoral JA. Org. Lett. 2008; 10: 4995
• 5x Dang D, Wu P, He C, Xie Z, Duan C. J. Am. Chem. Soc. 2010; 132: 14321
• 5y Garcia JI, Herrerias CI, Lopez-Sanchez B, Mayoral JA, Reiser O. Adv. Synth. Catal. 2011; 353: 2691
• 5z Aldea L, Delso I, Hager M, Glos M, Garcia JI, Mayoral JA, Reiser O. Tetrahedron 2012; 68: 3417
• 5aa See also ref. 7
• 6 Arai T, Sato T, Kanoh H, Kaneko K, Oguma K, Yanagisawa A. Chem.–Eur. J. 2008; 14: 882
• 7 Shi LX, Wu C.-D. Chem. Commun. 2011; 47: 2928
• 8 The Lewis acidic {[Cu(bpy)(BF₄)₂(H₂O)₂](bpy)} _n did not promote the Henry reaction
• 9 Osako T, Uozumi Y. Chem. Lett. 2009; 38: 902
• 10a Rabu P, Huang Z.-L, Hornick C, Drillon M. Synth. Met. 2001; 122: 509
• 10b Seki K, Mori W. J. Phys. Chem. B 2002; 106: 1380
• 10c Eddaoudi M, Kim J, Vodak D, Sudik A, Wachter J, O’Keeffe M, Yaghi OM. Proc. Natl. Acad. Sci. U.S.A. 2002; 99: 4900
• 10d Zhang S.-Y, Yu M.-X, Zhu L.-G. J. Mol. Struct. 2004; 101: 699
• 10e Pisklak TJ, MacíLas M, Coutinho DH, Huang RS, Balkus KJ. Jr. Top. Catal. 2006; 38: 269
• 10f Burger K.-S, Chaudhuri P, Wieghardt K, Nuber B. Chem.–Eur. J. 1995; 1: 583
• 10g Pichon A, Fierro CM, Nieuwenhuyzen M, James SL. CrystEngComm 2007; 9: 449
• 10h Yu J.-H, Wang Z.-M, Luo X.-Z, Du H.-G. Chin. J. Chem. 2008; 26: 1826
• 10i Furukawa H, Kim J, Ockwig NW, O’Keeffe M, Yaghi OM. J. Am. Chem. Soc. 2008; 130: 11650
• 10j Lin HY, Wang XL, Hu HL, Chen BK. Liu G. C. Solid State Sci. 2009; 11: 643
• 10k Sun C.-Y, Dong B, Lv Q, Zheng X.-J. Z. Anorg. Allg. Chem. 2011; 637: 276
• 11 Cu(4,4′-O₂CC₆H₄C₆H₄CO₂)·1/2 TED reported in ref. 10b showed a similar PXRD pattern with our Cu-carboxylate MOF
• 12 Hamada T, Ye X, Stahl SS. J. Am. Chem. Soc. 2008; 130: 833

For general reviews, see:
• 13a Rosini G. Comprehensive Organic Synthesis . Trost BM, Fleming I, Heathcock CH. Pergamon; New York: 1991. Vol. 2 321
• 13b Luzzio FA. Tetrahedron 2001; 57: 915
• 13c Ono N. The Nitro Group in Organic Synthesis . Wiley-VCH; New York: 2001

For reviews on the advance of catalytic Henry reaction, see:
• 14a Shibasaki M, Gröger H. Comprehensive Asymmetric Catalysis . Jacobsen EN, Pfaltz A, Yamamoto H. Springer; Berlin: 1999. Vol. III 1075
• 14b Shibasaki M, Gröger H, Kanai M. Comprehensive Asymmetric Catalysis . Jacobsen EN, Pfaltz A, Yamamoto H. Springer; Heidelberg: 2004. Suppl. 1 131-133
• 14c Palomo C, Oiarbide M, Mielgo A. Angew. Chem. Int. Ed. 2004; 43: 5442
• 14d Palomo C, Oiarbide M, Laso A. Eur. J. Org. Chem. 2007; 2561
• 15 An example of nanomagnet-functionalized MOF: Lohe MR, Gadrich K, Freudenberg T, Kockrick E, Dellmann T, Kaskel S. Chem. Commun. 2011; 47: 3075