A Highly Efficient Heterogeneous Copper-Catalyzed Oxidative Cyclization of Benzylamines and 1,3-Dicarbonyl Compounds To Give Trisubstituted Oxazoles

Abstract

The heterogeneous copper-catalyzed cascade oxidative cyclization between benzylamines and 1,3-dicarbonyl compounds was achieved by using the 3-(2-aminoethylamino)propyl-functionalized MCM-41-immobilized copper(II) complex [MCM-41-2N-Cu(OAc)₂] as catalyst and t-BuOOH (TBHP) as oxidant, with iodine as additive, under mild conditions, yielding a wide variety of 2,4,5-trisubstituted oxazoles in mostly good to excellent yields. This heterogeneous copper catalyst can be facilely prepared via a simple two-step procedure from readily available and inexpensive reagents and exhibits a slightly higher activity than Cu(OAc)₂. MCM-41-2N-Cu(OAc)₂ is also easy to recover and can be recycled up to eight times with almost consistent activity. The reaction is the first example of heterogeneous copper-catalyzed intermolecular cyclization for the construction of polysubstituted oxazoles.

Key words

copper - 2,4,5-trisubstituted oxazole - oxidative cyclization - heterogeneous catalysis - cascade reaction

• References

• 1a Wipf P. Chem. Rev. 1995; 95: 2115
• 1b Hughes RA, Moody CJ. Angew. Chem. Int. Ed. 2007; 46: 7930
• 1c Heng S, Gryncel KR, Kantrowitz ER. Bioorg. Med. Chem. 2009; 17: 3916
• 1d Davyt D, Serra G. Mar. Drugs 2010; 8: 2755
• 1e Zhang J, Ciufolini MA. Org. Lett. 2009; 11: 2389
• 1f Jin Z. Nat. Prod. Rep. 2011; 28: 1143
• 2a Forsyth CJ, Ahmed F, Cink RD, Lee CS. J. Am. Chem. Soc. 1998; 120: 5597
• 2b Vedejs E, Barda DA. Org. Lett. 2000; 2: 1033
• 2c Burgett AW. G, Li Q, Wei Q, Harran PG. Angew. Chem. Int. Ed. 2003; 42: 4961
• 2d Jin Z. Nat. Prod. Rep. 2006; 23: 464
• 2e Jin Z. Nat. Prod. Rep. 2009; 26: 382
• 3a Yeh VS. C. Tetrahedron 2004; 60: 11995
• 3b Riego E, Hernandez D, Albericio F, Alvarez M. Synthesis 2005; 1907
• 3c Anderson BA, Becke LM, Booher RN, Flaugh ME, Harn NK, Kress TJ, Varie DL, Wepsiec JP. J. Org. Chem. 1997; 62: 8634
• 3d Momose Y, Maekaawa T, Yamano T, Kawada M, Odaka H, Ikeda H, Sohda T. J. Med. Chem. 2002; 45: 1518
• 3e Patel HA, Ko D, Yavuz CT. Chem. Mater. 2014; 26: 6729
• 3f Jones RC, Chojnacka MW, Quail JW, Gardiner MG, Decken A, Yates BF, Gossage RA. Dalton Trans. 2011; 40: 1594
• 4a Turchi IJ, Dewar MJ. S. Chem. Rev. 1975; 75: 389
• 4b Revuelta J, Machetti F, Cicchi S. In Modern Heterocyclic Chemistry, Vol. 2. Alvarez-Builla J, Vaquero JJ, Barluenga J. Wiley-VCH; Weinheim: 2011
• 4c Shi B, Blake AJ, Lewis W, Campbell IB, Judkins BD, Moody CJ. J. Org. Chem. 2010; 75: 152
• 4d Xue W.-J, Li Q, Zhu Y.-P, Wang J.-G, Wu A.-X. Chem. Commun. 2012; 48: 3485
• 4e Zheng Y, Li X, Ren C, Zhang-Negrerie D, Du Y, Zhao K. J. Org. Chem. 2012; 77: 10353
• 4f Selvi T, Srinivasan K. Chem. Commun. 2014; 50: 10845
• 4g Weng Y, Lv W, Wu J, Ge B, Cheng G. Org. Lett. 2018; 20: 1853

For selected examples, see:
• 5a Merkul E, Muller TJ. J. Chem. Commun. 2006; 4817
• 5b Pan Y, Zheng F, Lin H, Zhan Z. J. Org. Chem. 2009; 74: 3148
• 5c Cheung CW, Buchwald SL. J. Org. Chem. 2012; 77: 7526
• 5d Wang Y.-F, Chen H, Zhu X, Chiba S. J. Am. Chem. Soc. 2012; 134: 11980
• 5e Senadi GC, Hu W.-P, Hsiao J.-S, Vandavasi J.-K, Chen C.-Y, Wang J.-J. Org. Lett. 2012; 14: 4478
• 5f Hu Y, Yi R, Wang C, Xin X, Wu F, Wan B. J. Org. Chem. 2014; 79: 3052
• 5g Zhou R.-R, Cai Q, Li D.-K, Zhuang S.-Y, Wu Y.-D, Wu A.-X. J. Org. Chem. 2017; 82: 6454

For selected examples, see:
• 6a Meyers AI, Tavares FX. J. Org. Chem. 1996; 61: 8207
• 6b Phillips AJ, Uto Y, Wipf P, Reno MJ, Williams DR. Org. Lett. 2000; 2: 1165
• 6c Williams DR, Lowder PD, Gu Y.-G, Brooks DA. Tetrahedron Lett. 1997; 38: 331
• 6d Wang Y, Li Z, Huang Y, Tang C, Wu X, Xu J, Yao H. Tetrahedron 2011; 67: 7406
• 6e Huang Y, Ni L, Gan F, He Y, Xu J, Wu X, Yao H. Tetrahedron 2011; 67: 2066
• 6f Li X, Li C, Yin B, Liu P, Li J, Shi Z. Chem. Asian J. 2013; 8: 1408
• 7a Alberico D, Scott MK, Lauten M. Chem. Rev. 2007; 107: 174
• 7b Flegeau EF, Popkin ME, Greaney MF. Org. Lett. 2006; 8: 2495
• 7c Lee K, Counceller CM, Stambuli JP. Org. Lett. 2009; 11: 1457
• 7d Williams DR, Fu LF. Org. Lett. 2010; 12: 808
• 7e Zhang ML, Zhang SH, Liu MC, Cheng J. Chem. Commun. 2011; 47: 11522
• 7f Shen X.-B, Zhang Y, Chen W.-X, Xiao Z.-K, Hu T.-T, Shao L.-X. Org. Lett. 2014; 16: 1984
• 8a Hashmi AS. K, Weyrauch JP, Frey W, Bats JW. Org. Lett. 2004; 6: 4391
• 8b Weyrauch JP, Hashmi AS. K, Schuster A, Hengst T, Schetter S, Littmann A, Rodolph M, Hamzic M, Visus J, Rominger F, Frey W, Bats JW. Chem. Eur. J. 2010; 16: 956
• 8c Hashmi AS. K, Blanco Jaimes MC, Schuster AM, Rominger F. J. Org. Chem. 2012; 77: 6394
• 8d Peng H, Akhmedov NG, Liang Y.-F, Jiao N, Shi X. J. Am. Chem. Soc. 2015; 137: 8912
• 8e Querard P, Girard SA, Uhlig N, Li C.-J. Chem. Sci. 2015; 6: 7332
• 8f Davies PW, Cremonesi A, Dumitrescu L. Angew. Chem. Int. Ed. 2011; 50: 8931
• 8g Luo Y, Ji K, Li Y, Zhang L. J. Am. Chem. Soc. 2012; 134: 17412
• 8h Chen M, Sun N, Chen H, Liu Y. Chem. Commun. 2016; 52: 6324
• 9a Arcadi A, Cacchi S, Cacia L, Fabrizi G, Marinelli F. Org. Lett. 2001; 3: 2501
• 9b Zheng J, Zhang M, Huang L, Hu X, Wu W, Huang H, Jiang H. Chem. Commun. 2014; 50: 3609
• 10a Davies JR, Kane PD, Moody CJ. J. Org. Chem. 2005; 70: 7305
• 10b Lee YR, Yeon SH, Seo Y, Kim BS. Synthesis 2004; 2787
• 11a Milton MD, Inada Y, Nishibayashi Y, Uemura S. Chem. Commun. 2004; 2712
• 11b Chatterjee T, Cho JY, Cho EJ. J. Org. Chem. 2016; 81: 6995
• 12a Borduas N, Powell DA. J. Org. Chem. 2008; 73: 7822
• 12b Boldron C, Gamez P, Tooke DM, Spek AL, Reedijk J. Angew. Chem. Int. Ed. 2005; 44: 3585
• 12c Li Z.-P, Li C.-J. J. Am. Chem. Soc. 2005; 127: 3672
• 12d Li Z.-P, Li C.-J. J. Am. Chem. Soc. 2005; 127: 6968
• 12e Basle O, Li C.-J. Green Chem. 2007; 9: 1047
• 12f Li C.-J. Acc. Chem. Res. 2009; 42: 335
• 13a Beletskaya IP, Chepakov AV. Coord. Chem. Rev. 2004; 248: 2337
• 13b Ley SV, Thomas AW. Angew. Chem. Int. Ed. 2003; 42: 5400
• 13c Chemler SR, Fuller PH. Chem. Soc. Rev. 2007; 36: 1153
• 13d Martin R, Rodriguez-Rivero M, Buchwald SL. Angew. Chem. Int. Ed. 2006; 45: 7079
• 13e Jones CP, Anderson KW, Buchwald SL. J. Org. Chem. 2007; 72: 7968
• 13f Rodriguez-Rivero M, Buchwald SL. Org. Lett. 2007; 9: 973
• 14a Martin R, Cuenca A, Buchwald SL. Org. Lett. 2007; 9: 5521
• 14b Wan C, Zhang J, Wang S, Fan J, Wang Z. Org. Lett. 2010; 12: 2338
• 14c Cano I, Alvarez E, Nicasio MC, Perez PJ. J. Am. Chem. Soc. 2011; 133: 191
• 14d Li X, Huang L, Chen H, Wu W, Huang H, Jiang H. Chem. Sci. 2012; 3: 3463
• 14e Xu Z, Zhang C, Jiao N. Angew. Chem. Int. Ed. 2012; 56: 11367
• 14f Qi C, Peng Y, Wang L, Ren Y, Jiang H. J. Org. Chem. 2018; 83: 11926
• 14g Pan J, Li X, Qiu X, Luo X, Jiao N. Org. Lett. 2018; 20: 2762
• 15a Girard C, Onen E, Aufort M, Beauviere S, Samson E, Herscovici J. Org. Lett. 2006; 8: 1689
• 15b Chassaing S, Sido AS. S, Alix A, Kumarraja M, Pale P, Sommer J. Chem. Eur. J. 2008; 14: 6713
• 15c Lipshutz BH, Taft BR. Angew. Chem. Int. Ed. 2006; 45: 8235
• 15d Wang D, Etienne L, Echeverria M, Moya S, Astruc D. Chem. Eur. J. 2014; 20: 4047
• 15e Yamada YM. A, Sarkar SM, Uozumi Y. J. Am. Chem. Soc. 2012; 134: 9285
• 15f Kantam ML, Reddy CV, Srinivas P, Bhargava S. In Topics in Organometallic Chemistry, Vol. 46. Taillefer M, Ma D. Springer; Heidelberg: 2013: 119-171
• 16a Wu Q, Wang L. Synthesis 2008; 2007
• 16b Zhang L, Li P, Wang L. Lett. Org. Chem. 2006; 3: 282
• 16c Xiao R, Yao R, Cai M. Eur. J. Org. Chem. 2012; 4178
• 16d Zhao H, Huang B, Wu Y, Cai M. J. Organomet. Chem. 2015; 797: 21
• 17a Chiang GC. H, Olsson T. Org. Lett. 2004; 6: 3079
• 17b Benyahya S, Monnier F, Taillefer M, Chi Man MW, Bied C, Ouazzan F. Adv. Synth. Catal. 2008; 350: 2205
• 17c Benyahya S, Monnier F, Chi Man MW, Bied C, Ouazzan F, Taillefer M. Green Chem. 2009; 11: 1121
• 17d Phan NT. S, Nguyen TT, Nguyen VT, Nguyen KD. ChemCatChem 2013; 5: 2374
• 17e Chouhan G, Wang D, Alper H. Chem. Commun. 2007; 4809
• 17f Zhao H, He W, Yao R, Cai M. Adv. Synth. Catal. 2014; 356: 3092
• 17g Zhao H, Jiang Y, Chen Q, Cai M. New J. Chem. 2015; 39: 2106
• 17h Zhao H, He W, Wei L, Cai M. Catal. Sci. Technol. 2016; 6: 1488
• 17i Pan S, Yan S, Osako T, Uozumi Y. ACS Sustain. Chem. Eng. 2017; 5: 10722
• 18a Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS. Nature 1992; 359: 710
• 18b Corma A. Top. Catal. 1997; 4: 249
• 18c Martin-Aranda RM, Cejka J. Top. Catal. 2010; 53: 141
• 19a Mehnert PC, Weaver DW, Ying JY. J. Am. Chem. Soc. 1998; 120: 12289
• 19b Kantam ML, Bandyopadhyay T, Rahman A, Reddy NM, Choudary BM. J. Mol. Catal. A: Chem. 1998; 133: 293
• 19c Mukhopadhyay K, Sarkar BR, Chaudhari RV. J. Am. Chem. Soc. 2002; 124: 9692
• 19d Cai M, Zheng G, Ding G. Green Chem. 2009; 11: 1687
• 19e Cai M, Peng J, Hao W, Ding G. Green Chem. 2011; 13: 190
• 19f Hao W, Liu H, Yin L, Cai M. J. Org. Chem. 2016; 81: 4244
• 19g Havasi F, Ghorbani-Choghamarani A, Nikpour F. New J. Chem. 2015; 39: 6504
• 20 Shyu S.-G, Cheng S.-W, Tzou D.-L. Chem. Commun. 1999; 2337
• 21a Nunes CD, Valente AA, Pillinger M, Fernandes AC, Romao CC, Rocha J, Goncalves IS. J. Mater. Chem. 2002; 12: 1735
• 21b Jia M, Seifert A, Thiel WR. Chem. Mater. 2003; 15: 2174
• 22a Corma A, Gutierrez-Puebla E, Iglesias M, Monge A, Perez-Ferreras S, Sanchez F. Adv. Synth. Catal. 2006; 348: 1899
• 22b Corma A, Gonzalez-Arellano C, Iglesias M, Navarro MT, Sanchez F. Chem. Commun. 2008; 6218
• 22c del Pozo C, Corma A, Iglesias M, Sanchez F. Organometallics 2010; 29: 4491
• 22d Villaverde G, Corma A, Iglesias M, Sanchez F. ACS Catal. 2012; 2: 399
• 22e Yang W, Zhang R, Yi F, Cai M. J. Org. Chem. 2017; 82: 5204
• 23 Lempers HE. B, Sheldon RA. J. Catal. 1998; 175: 62
• 24 Kumler WD. J. Am. Chem. Soc. 1938; 60: 855
• 25 Cai X.-H, Yang H.-J, Zhang G.-L. Synthesis 2005; 1569
• 26 Sanz-Cervera JF, Blasco R, Piera J, Cynamon M, Ibanez I, Murguia M, Fustero S. J. Org. Chem. 2009; 74: 8988
• 27 Verrier C, Fiol-Petit C, Hoarau C, Marsais F. Org. Biomol. Chem. 2011; 9: 6215
• 28 Whitney SE, Rickborn B. J. Org. Chem. 1991; 56: 3058