Diastereoselective Mannich reaction with prolinated MWCNTs as a heterogeneous organo-nanocatalyst

Abstract

We intended to convert proline as a homogeneous catalyst to a heterogeneous catalyst by prolination of MWCNTs to improve proline efficiency as a catalyst by the ease of separating, catalytic economy, reusability, etc. To reach these goals, we sketched Pro-MWCNT catalyst and characterized it by different analyses such as FT-IR, SEM, EDX, CHNS. The efficiency of this heterogeneous catalyst was investigated and compared with proline homogeneous catalyst in Mannich reaction. The results hold out improvements in stereoselectivity, ease of separating and reusability.

Graphic Abstract

This work represents an efficient and simple method to prepare Prolinated- MWCNTs as a heterogeneous organo-nanocatalyst. Prolinated-MWCNT was characterized by different analyses. The efficiency and catalytic activity of Pro-MWCNTs have investigated in mannich reaction, which has shown higher diastereoselectivity, moderate enantioselectivity, good reusability and high yields versus parent proline catalyst.

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References

  1. 1.

    Dalko P I and Moisan L 2004 In the golden age of organocatalysis Angew. Chem. Int. Ed. 43 5138

    CAS  Article  Google Scholar 

  2. 2.

    Dalko P I and Moisan L 2001 Enantioselective organocatalysis Angew. Chem. Int. Ed. 40 3726

    CAS  Article  Google Scholar 

  3. 3.

    Benaglia M, Puglisi A and Cozzi F 2003 Polymer-supported organic catalysts Chem. Rev. 103 3401

    CAS  Article  Google Scholar 

  4. 4.

    Houk K N and List B 2004 Asymmetric organocatalysis Acc. Chem. Res. Ed. 37 487

    CAS  Google Scholar 

  5. 5.

    Lelais G and MacMillan D W C 2007 In Enantioselective Organocatalysis: Reactions and Experimental Procedures P I Dalko (Ed.) (Weinheim: Wiley-VCH) p. 95

  6. 6.

    MacMillan D W C 2008 The advent and development of organocatalysis Nature 455 304

    CAS  PubMed  Google Scholar 

  7. 7.

    Kotsuki H, Ikishima H and Kuyama A 2008 Organocatalytic asymmetric synthesis using proline and related molecules Heterocycles 75 757

    CAS  Article  Google Scholar 

  8. 8.

    Bertelsen S and Jorgensen K A 2009 Organocatalysis—after the gold rush Chem. Soc. Rev. 38 2178

    CAS  Article  Google Scholar 

  9. 9.

    Xu L-W and Lu Y 2008 Primary amino acids: privileged catalysts in enantioselective organocatalysis Org. Biomol. Chem. 6 2047

    CAS  Article  Google Scholar 

  10. 10.

    Alcaide B, Almendros P, Luna A and Torres M R 2006 Proline-catalyzed diastereoselective direct aldol reaction between 4-oxoazetidine-2-carbaldehydes and ketones J. Org. Chem. 71 4818

    CAS  Article  Google Scholar 

  11. 11.

    Janey J M, Hsiao Y and Armstrong J D 2006 Proline-catalyzed asymmetric Mannich reactions in the synthesis of a DPP-IV inhibitor J. Org. Chem. 71 390

    CAS  Article  Google Scholar 

  12. 12.

    Ramachary D B, Chowdari N S and Barbas C F 3rd 2003 Organocatalytic asymmetric Domino Knoevenagel/Diels−Alder reactions: a bioorganic approach to the diastereospecific and enantioselective construction of highly substituted spiro[5.5]undecane-1,5,9-triones Angew. Chem. 115 4365

  13. 13.

    Bogevig A, Juhl K, Kumaragurubaran N, Zhuang W and Jorgensen K A 2002 Direct organo-catalytic asymmetric α-aminoation of aldehydes—a simple approach to optically active α-amino aldehydes, α- amino alcohols, and alif-amino acids Angew. Chem. Int. Ed. 41 1790

    CAS  Article  Google Scholar 

  14. 14.

    Oskooie H A, Roomizadeh E and Heravi M M 2006 Solvent-free Lproline catalysed condensation of ethyl cycnoacetate with aldehydes J. Chem. Res. 4 246

    Article  Google Scholar 

  15. 15.

    Li Y, Chen H, Shi Ch, Shi D and Ji Sh 2010 Efficient one-pot synthesis of spirooxindole derivatives catalyzed by l-proline in aqueous medium J. Comb. Chem. 12 231

    CAS  Article  Google Scholar 

  16. 16.

    Fu L, Lin W, Hu M H, Liu X C, Huang Z B and Shi D Q 2014 Efficient synthesis of functionalized benzo[b][1,8]naphthyridine derivatives via three-component reaction catalyzed by l-proline ACS Comb. Sci. 16 238

    CAS  Article  Google Scholar 

  17. 17.

    Zhu Y W, Yi W B and Cai C 2011 A recyclable fluoroalkylated 1,4-disubstituted [1,2,3]-triazole organocatalyst for aldol condensation of aldehydes and ketones J. Fluor. Chem. 132 71

    CAS  Article  Google Scholar 

  18. 18.

    Riente P, Yadav J and Pericàs M A 2012 A click strategy for the immobilization of macmillan organocatalysts onto polymers and magnetic nanoparticles Org. Lett. 14 3668

    CAS  Google Scholar 

  19. 19.

    Miura T, Imai K, Ina M, Tada N, Imai N and Itoh A 2010 Direct asymmetric aldol reaction with recyclable fluorous organocatalyst Org. Lett. 12 1620

    CAS  Google Scholar 

  20. 20.

    Benaglia M 2006 Recoverable and recyclable chiral organic catalysts New J. Chem. 30 1525

    CAS  Google Scholar 

  21. 21.

    Kristensen T E, Vestli K, Jakobsen M G, Hansen F K and Hansen T A 2010 General approach for preparation of polymer-supported chiral organocatalysts via acrylic copolymerization J. Org. Chem. 75 1620

    CAS  Article  Google Scholar 

  22. 22.

    Shylesh S, Zhou Z, Meng Q, Wagener A, Seifert A, Ernst S and Thiel W R 2010 Sustainable, green protocols for heterogenized organocatalysts: N-Phenylthiazolium salts heterogenized on organic–inorganic hybrid mesoporous supports J. Mol. Catal. A Chem. 332 65

    CAS  Article  Google Scholar 

  23. 23.

    Zeng T, Yang L, Hudson R, Song G, Moores A R and Li C-J 2011 Fe3O4 nanoparticle-supported copper(I) pybox catalyst: magnetically recoverable catalyst for enantioselective direct-addition of terminal alkynes to imines Org. Lett. 13 442

    CAS  Google Scholar 

  24. 24.

    Su D S, Perathoner S and Centi G 2013 Nanocarbons for the development of advanced catalysts Chem. Rev. 113 5782

    CAS  Article  Google Scholar 

  25. 25.

    Yu R, Ran M, Wen J, Sun W, Chu W, Jiang C and He Z 2015 The effect of hydroxylation on CNT to form Chitosan-CNT composites: a DFT study Appl. Surf. Sci. 359 643

    CAS  Article  Google Scholar 

  26. 26.

    Eshghi H, Rahimizadeh M, Hosseini M and Javadian-Saraf A 2013 Diastereoselective three-component Mannich reaction catalyzed by silica supported ferric hydrogensulfate Monatsh. Chem. 144 197

    CAS  Google Scholar 

  27. 27.

    Eshghi H, Rahimizadeh M, Eshkil F, Hosseini M, Bakavoli M and Sanei-Ahmadabad M 2014 Synthesis of novel bis(β-aminocarbonyl) compounds and some β-aminocarbonyls by catalyst-free multicomponent Mannich reactions J. Iran Chem. Soc. 11 685

    CAS  Article  Google Scholar 

  28. 28.

    Kamble S, Kumbhar A, Rashinkar G, Barge M and Salunkhe R 2012 Ultrasound promoted efficient and green synthesis of b-amino carbonyl compounds in aqueous hydrotropic medium Ultrasonics Sonochem. 19 812

    CAS  Article  Google Scholar 

  29. 29.

    Jin Y, Hawkins S C, Huynh Ch P and Su Sh 2013 Carbon nanotube modified carbon composite monoliths as superior adsorbents for carbon dioxide capture Energy Environ. Sci. 6 2591

    CAS  Article  Google Scholar 

  30. 30.

    Nasresfahani Z, Kassaee M Z, Nejati-Shendi M, Eidi E and Taheri Q 2016 Mesoporous silica nanoparticles (MSNs) as an efficient and reusable nanocatalyst for synthesis of β-amino ketones through one-pot three component Mannich reactions RSC Adv. 6 32183

  31. 31.

    Khoshnavazi R, Bahrami L, Havasi F and Naseri E 2017 H3PW12O40 supported on functionalized polyoxometalate organic–inorganic hybrid nanoparticles as efficient catalysts for three component Mannich-type reactions in water RSC Adv. 7 11510

  32. 32.

    Dong F, Zhenghao F and Zuliang L 2009 Functionalized ionic liquid as the recyclable catalyst for Mannich-type reaction in aqueous media Catal. Commun. 10 1267

    CAS  Google Scholar 

  33. 33.

    Li-li J and Yun-tao L 2013 One-pot Three-component Mannich reaction catalyzed by 2-hydroxylpyridine Chem. Res. Chin. Univ. 29 710

    Article  Google Scholar 

  34. 34.

    Mansoori A, Eshghi H and Lari J 2018 An efficient synthesis of 1,3-diphenyl-3-phenylamino-propan-1-one and its derivatives by Mannich reaction in the presence of doped porous carbon by nitrogen and sulfur (NS-PCS) as catalyst J. Chin. Chem. Soc. 65 548

  35. 35.

    Hojjati-Rad M, Eshghi H, Seyyedi, S M, Rahimizadeh M, Eshkil M and Lamei K 2016 One-pot three-component kinetic controlled and syn-diastereoselective Mannich reaction of unfunctionalized ketones in water catalyzed by nano-manganese hydrogen sulfate particles J. Iran Chem. Soc. 13 1105

    CAS  Article  Google Scholar 

  36. 36.

    Eshghi H, Rahimizadeh M, Javadian-Saraf A and Hosseini M 2015 Nano-manganese hydrogen sulfate as a novel catalyst for the anti-diastereoselective Mannich reaction in water Res. Chem. Intermed. 41 5049

    CAS  Article  Google Scholar 

  37. 37.

    Liua Zh, Liub Y and Pengc D 2016 Hydroxylation of multi-walled carbon nanotubes: Enhanced biocompatibility through reduction of oxidative stress initiated cell membrane damage, cell cycle arrestment and extrinsic apoptotic pathway Environ. Toxicol. Pharmacol. 47 124

    Article  Google Scholar 

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Acknowledgements

The authors gratefully acknowledge the vice-chancellor- Affairs of Research of Ferdowsi University of Mashhad for financial support by (Grant No. 3/47784).

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Correspondence to Hossein Eshghi.

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This article is dedicated to the memory of, Professor Mehdi Bakavoli, who recently passed away.

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Khoshnevis, M., Eshghi, H. Diastereoselective Mannich reaction with prolinated MWCNTs as a heterogeneous organo-nanocatalyst. J Chem Sci 132, 41 (2020). https://doi.org/10.1007/s12039-020-1740-4

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Keywords

  • Multiwall Carbon Nanotubes
  • L-proline
  • Diastereoselective
  • Mannich reaction
  • Heterogeneous Catalyst