Abstract
In this study a novel, effective and recoverable Cu(II)-catalyst was synthesized by incorporating of Cu(OAc)2 within ethanolamine-triazine derivative (TAETA) attached to chitosan (Chs)-functionalized γ-Fe2O3 nanoparticles [MNP@Chs/TAETA-Cu(II)]. It was characterized by different techniques such as FT-IR, EDS, ICP, TEM, TGA and VSM. The as-prepared nanocomposite demonstrated high oxidation activity and desired selectivity in the aerobic oxidation of structurally diverse set of benzyl alcohols. Spectral results and leaching experiments revealed that this magnetically recoverable heterogeneous catalyst preserved its structure after it was reused several times. This protocol offers some beneficial features such as the use of oxygen as an ideal oxidant, stability of nanocomplex, easily catalyst separation by using an external magnetic field and efficient recycling as well as the lack of by-products.
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Musawir M, Davey PN, Kelly G, Kozhevnikov IV (2003) Highly efficient liquid-phase oxidation of primary alcohols to aldehydes with oxygen catalysed by Ru–Co oxide. Chem Commun. https://doi.org/10.1039/B212585B
Guo Z, Liu B, Zhang Q et al (2014) Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry. Chem Soc Rev 43:3480–3524
Sheldon RA, Arends IWCE, ten Brink G-J, Dijksman A (2002) Green, catalytic oxidations of alcohols. Acc Chem Res 35:774–781
Lou J-D, Xu Z-N (2002) Selective oxidation of primary alcohols with chromium trioxide under solvent free conditions. Tetrahedron Lett 43:6095–6097
Taylor RJK, Reid M, Foot J, Raw SA (2005) Tandem oxidation processes using manganese dioxide: discovery, applications, and current studies. Acc Chem Res 38:851–869
Uyanik M, Ishihara K (2009) Hypervalent iodine-mediated oxidation of alcohols. Chem Commun. https://doi.org/10.1039/B823399C
Tojo G, Fernández MI (2006) Oxidation of alcohols to aldehydes and ketones: a guide to current common practice. Springer Science & Business Media, New York
Parmeggiani C, Cardona F (2012) Transition metal based catalysts in the aerobic oxidation of alcohols. Green Chem 14:547–564
Parmeggiani C, Matassini C, Cardona F (2017) A step forward towards sustainable aerobic alcohol oxidation: new and revised catalysts based on transition metals on solid supports. Green Chem 19:2030–2050
Velusamy S, Punniyamurthy T (2004) Novel vanadium-catalyzed oxidation of alcohols to aldehydes and ketones under atmospheric oxygen. Org Lett 6:217–219
Sharma VB, Jain SL, Sain B (2003) Cobalt phthalocyanine catalyzed aerobic oxidation of secondary alcohols: an efficient and simple synthesis of ketones. Tetrahedron Lett 44:383–386
Sun X, Li X, Song S et al (2015) Mn-catalyzed highly efficient aerobic oxidative hydroxyazidation of olefins: a direct approach to β-azido alcohols. J Am Chem Soc 137:6059–6066
Martín SE, Suárez DF (2002) Catalytic aerobic oxidation of alcohols by Fe(NO3)3-FeBr3. Tetrahedron Lett 43:4475–4479
Xu B, Lumb J-P, Arndtsen BA (2015) A TEMPO-free copper-catalyzed aerobic oxidation of alcohols. Angew Chemie 127:4282–4285
Velusamy S, Ahamed M, Punniyamurthy T (2004) Novel polyaniline-supported molybdenum-catalyzed aerobic oxidation of alcohols to aldehydes and ketones. Org Lett 6:4821–4824
Schultz MJ, Hamilton SS, Jensen DR, Sigman MS (2005) Development and comparison of the substrate scope of Pd-catalysts for the aerobic oxidation of alcohols. J Org Chem 70:3343–3352
Personick ML, Zugic B, Biener MM et al (2015) Ozone-activated nanoporous gold: a stable and storable material for catalytic oxidation. ACS Catal 5:4237–4241
McCann SD, Stahl SS (2015) Copper-catalyzed aerobic oxidations of organic molecules: pathways for two-electron oxidation with a four-electron oxidant and a one-electron redox-active catalyst. Acc Chem Res 48:1756–1766
Wendlandt AE, Suess AM, Stahl SS (2011) Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights. Angew Chemie Int Ed 50:11062–11087
Saberikia I, Safaei E, Karimi B, Lee Y-I (2017) A novel copper complex of proline-based mono (phenol) amine ligand (Hlpro) immobilized in SBA-15 as a model catalyst of galactose oxidase. ChemistrySelect 2:11164–11171
Jiang N, Ragauskas AJ (2005) Copper(II)-catalyzed aerobic oxidation of primary alcohols to aldehydes in ionic liquid [bmpy] PF6. Org Lett 7:3689–3692
Hoover JM, Steves JE, Stahl SS (2012) Copper(I)/TEMPO-catalyzed aerobic oxidation of primary alcohols to aldehydes with ambient air. Nat Protoc 7:1161
Gamba I, Mutikainen I, Bouwman E et al (2013) Synthesis and characterization of copper complexes of a tetrapyridyl ligand, and their use in the catalytic aerobic oxidation of benzyl alcohol. Eur J Inorg Chem 2013:115–123
Hill NJ, Hoover JM, Stahl SS (2012) Aerobic alcohol oxidation using a copper(I)/TEMPO catalyst system: a green, catalytic oxidation reaction for the undergraduate organic chemistry laboratory. J Chem Educ 90:102–105
Ryland BL, Stahl SS (2014) Practical aerobic oxidations of alcohols and amines with homogeneous copper/TEMPO and related catalyst systems. Angew Chemie Int Ed 53:8824–8838
Ansari IA, Gree R (2002) TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6]. Org Lett 4:1507–1509
Liu Z, Shen Z, Zhang N et al (2018) Aerobic oxidation of alcohols catalysed by Cu(I)/NMI/TEMPO system and its mechanistic insights. Catal Lett 148:2709–2718
Fernandes AE, Riant O, Jonas AM, Jensen KF (2016) One “click” to controlled bifunctional supported catalysts for the Cu/TEMPO-catalyzed aerobic oxidation of alcohols. RSC Adv 6:36602–36605
Wang L, Bie Z, Shang S et al (2018) Cu-catalyzed aerobic oxidation of alcohols with a multi-functional NMI-TEMPO. ChemistrySelect 3:3386–3390
Lagerspets E, Lagerblom K, Heliövaara E et al (2019) Schiff base Cu(I) catalyst for aerobic oxidation of primary alcohols. Mol Catal 468:75–79
Feng X, Lv P, Sun W et al (2017) Reduced graphene oxide-supported Cu nanoparticles for the selective oxidation of benzyl alcohol to aldehyde with molecular oxygen. Catal Commun 99:105–109
Polshettiwar V, Luque R, Fihri A et al (2011) Magnetically recoverable nanocatalysts. Chem Rev 111:3036–3075
Ranganath KVS, Glorius F (2011) Superparamagnetic nanoparticles for asymmetric catalysis–a perfect match. Catal Sci Technol 1:13–22
Lim CW, Lee IS (2010) Magnetically recyclable nanocatalyst systems for the organic reactions. Nano Today 5:412–434
Saiyed ZM, Sharma S, Godawat R et al (2007) Activity and stability of alkaline phosphatase (ALP) immobilized onto magnetic nanoparticles (Fe3O4). J Biotechnol 131:240–244
Jafarpour M, Rezaeifard A, Yasinzadeh V, Kargar H (2015) Starch-coated maghemite nanoparticles functionalized by a novel cobalt Schiff base complex catalyzes selective aerobic benzylic C-H oxidation. RSC Adv 5:38460–38469
Cuong ND, Hoa TT, Khieu DQ et al (2012) Synthesis, characterization, and comparative gas-sensing properties of Fe2O3 prepared from Fe3O4 and Fe3O4-chitosan. J Alloys Compd 523:120–126
Al-Sagheer FA, Merchant S (2011) Visco-elastic properties of chitosan-titania nano-composites. Carbohydr Polym 85:356–362
Hoover JM, Ryland BL, Stahl SS (2013) Copper/TEMPO-catalyzed aerobic alcohol oxidation: mechanistic assessment of different catalyst systems. ACS Catal 3:2599–2605
Duan RF, Cheng L, Zhang QC et al (2015) Mechanistic insight into the aerobic oxidation of benzyl alcohol catalyzed by the Cu II-TEMPO catalyst in alkaline water solution. RSC Adv 5:83976–83984
Hossain MM, Shyu S-G (2010) Efficient and selective aerobic alcohol oxidation catalyzed by copper(II)/2,2,6,6,-tetramethylpiperidine-1-oxyl at room temperature. Adv Synth Catal 352:3061–3068
Zhu X, Yang D, Wei W et al (2014) Magnetic copper ferrite nanoparticles/TEMPO catalyzed selective oxidation of activated alcohols to aldehydes under ligand-and base-free conditions in water. RSC Adv 4:64930–64935
Samanta S, Das S, Samanta PK et al (2013) A mononuclear copper(II) complex immobilized in mesoporous silica: an efficient heterogeneous catalyst for the aerobic oxidation of benzylic alcohols. RSC Adv 3:19455–19466
Herbert M, Montilla F, Galindo A (2010) Supercritical carbon dioxide, a new medium for aerobic alcohol oxidations catalysed by copper-TEMPO. Dalton Trans 39:900–907
Pan S, Yan S, Osako T, Uozumi Y (2018) Controlled aerobic oxidation of primary benzylic alcohols to aldehydes catalyzed by polymer-supported triazine-based dendrimer-copper composites. Synlett 29:1152–1156
Zhao H, Chen Q, Wei L et al (2015) A highly efficient heterogeneous aerobic alcohol oxidation catalyzed by immobilization of bipyridine copper(I) complex in MCM-41. Tetrahedron 71:8725–8731
Li L, Matsuda R, Tanaka I et al (2014) A crystalline porous coordination polymer decorated with nitroxyl radicals catalyzes aerobic oxidation of alcohols. J Am Chem Soc 136:7543–7546
Ahmad JU, Figiel PJ, Räisänen MT et al (2009) Aerobic oxidation of benzylic alcohols with bis (3,5-di-tert-butylsalicylaldimine) copper(II) complexes. Appl Catal A 371:17–21
Albadi J, Alihoseinzadeh A, Mansournezhad A (2015) Aerobic oxidation of alcohols catalyzed by a new ZnO-supported copper oxide nanocatalyst in aqueous media. Synth Commun 45:877–885
Taher A, Kim DW, Lee I-M (2017) Highly efficient metal organic framework (MOF)-based copper catalysts for the base-free aerobic oxidation of various alcohols. RSC Adv 7:17806–17812
Kim BR, Oh JS, Kim J, Lee CY (2015) Aerobic oxidation of alcohols over copper-containing metal-organic frameworks. Bull Korean Chem Soc 36:2799–2800
Li J, Gao H, Tan L et al (2016) Superparamagnetic core-shell metal-organic framework Fe3O4/Cu3(BTC)2 microspheres and their catalytic activity in the aerobic oxidation of alcohols and olefins. Eur J Inorg Chem 2016:4906–4912
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Support for this work by Research Council of University of Birjand is highly appreciated.
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Hasanpour, B., Jafarpour, M., Feizpour, F. et al. Copper(II)-Ethanolamine Triazine Complex on Chitosan-Functionalized Nanomaghemite for Catalytic Aerobic Oxidation of Benzylic Alcohols. Catal Lett 151, 45–55 (2021). https://doi.org/10.1007/s10562-020-03298-6
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DOI: https://doi.org/10.1007/s10562-020-03298-6
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