Nitrilimine cycloadditions catalyzed by iron oxide nanoparticles
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Nitrilimine cycloadditions to ethylenes, acetylenes, and activated nitriles have been exploited in the presence of catalytic amounts of oleic-acid-coated iron oxide nanoparticles (diameter = 11.9 ± 1.0 nm). The reactions were fully regioselective with monosubstituted ethylenes and ethyl cyanoformiate, while mixtures of cycloadducts were obtained in the presence of methyl propiolate. The intervention of iron oxide nanoparticles allowed carrying out the cycloadditions at milder conditions compared to the metal-free thermal processes. A labile intermediate has been proposed to explain this behavior.
KeywordsDipolar cycloadditions Nitrilimines Catalysis Magnetic nanoparticles Nanoparticle catalysis
The authors are grateful to F. Cargnoni (ISTM-CNR, Milan) for useful suggestions about the DFT calculations.
G.M. and A.P. together conceived and planned the research, discussed the results, and wrote the manuscript. G.M. carried out all the cycloadditions. A.M.F. and S.M. synthesized the nanoparticles and A.M.F. characterized them. A.P. carried out the calculations. All the authors read and approved the final manuscript.
This study was funded by Regione Lombardia (RSPPTECH Project); the Italian MIUR under grant FIRB RBAP115AYN (oxides at the nanoscale: multifunctionality and applications) and the Department of Chemistry of UNIMI under grant PSR2015-1716FDEMA_09 (cycloaddition reactions catalyzed by metal oxide nanoparticles: NANOCAT).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- Alemagna A, Del Buttero P, Licandro E et al (1981) Inter- and intra-molecular reactions of arylazomethylenetriphenylphosphoranes with unsaturated carbon-carbon bonds. Gazz Chim Ital 111:285–288Google Scholar
- Bertini, I, Gray HB, Lippard S et al (1994) Bioinorganic chemistry, University Science Books: Mill Valley, 1994Google Scholar
- Caramella P, Grünanger P (1984) 1,3-Dipolar Cycloaddition Chemistry,Wiley: New York, Vol. 1, Ch. 3Google Scholar
- Cargnoni F, Molteni G, Cooper DL, Raimondi M, Ponti A (2006) The electronic structure of nitrilimine: absence of the carbenic form. Chem Commun:1030–1032Google Scholar
- Cocco MT, Maccioni A, Plumitallo A (1985) Phytotoxic activity in pyrazole derivatives II. Farmaco Sci 40:272–284Google Scholar
- De La Mare PBD, Swedlund BE (1973) The chemistry of the carbon-halogen bond, John Wiley & Sons: London, Part 1, Ch. 7, pp. 407–458Google Scholar
- Elguero J, Goya P, Jagerovic N et al (2002) Pyrazoles as drugs: facts and fantasies. Targets Heterocycl Syst 6:52–98Google Scholar
- Frisch MJ, Trucks GW, Schlegel HB et al (2009) Gaussian 09, Revision C.01, Gaussian Inc.: WallingfordGoogle Scholar
- Fusco R, Romani R (1946) Investigations of formazyls. I. The action of diazo compounds on chloro- and bromomalonic acids. Gazz Chim Ital 76:419–438Google Scholar
- Huisgen R (1984) 1,3-Dipolar cycloaddition chemistry, Wiley: New York, Vol. 1, Ch. 1Google Scholar
- Marshak S (2005) The earth: portrait of a planet. W.W. Norton & Co., New YorkGoogle Scholar
- Meyers AI, Sircar CJ (1970) The chemistry of the cyano group. Wiley-Interscience, London, Ch 8Google Scholar
- Molteni G (2007) Silver(I) salts as useful reagents in pyrazole synthesis. ARKIVOC (2):224–246Google Scholar
- Molteni G, Garanti L (2001) Behavior of hydrazonoyl chlorides towards the C=N double bond of Δ2-pyrazolines. A study on 2-(4-nitrophenyl)-2,3,3a,4,5,6-hexahydro-6-oxofuro[3,4-c]zpyrazole. Heterocycles 55:1573–1580Google Scholar
- Mondini S, Ferretti AM, Puglisi A et al (2012) Pebbles and Pebblejuggler: software for accurate, unbiased, and fast measurement and analysis of nanoparticle morphology from transmission electron microscopy (TEM) micrographs. Nanoscale 4:5356–5372 Pebbles is freely available from the authors, http://pebbles.istm.cnr.it CrossRefGoogle Scholar
- Padwa A (1992) Comprehensive organic synthesis. Pergamon Press, New York, 1992, Vol. 4, Ch. 4–9, p 1069Google Scholar
- Penning TD, Talley JJ, Bertenshaw SR, Carter JS, Collins PW, Docter S, Graneto MJ, Lee LF, Malecha JW, Miyashiro JM, Rogers RS, Rogier DJ, Yu SS, Anderson GD, Burton EG, Cogburn JN, Gregory SA, Koboldt CM, Perkins WE, Seibert K, Veenhuizen AW, Zhang YY, Isakson PC (1997) Synthesis and biological evaluation of the 1,5-diarylpyrazole class of cyclooxygenase-2 inhibitors: identification of 4-[5-(4-methylphenyl)-3-(trifluoromethyl)-1H-pyrazol-1-yl]benzene sul fonamide (SC-58635, Celecoxib). J Med Chem 40:1347–1365CrossRefGoogle Scholar
- Reddy PM, Kumar KA, Raju KM et al (2000) Synthesis and characterization of iron (II, III) complexes of 3-hydroxy-benzaldehyde isonicotinic acid hydrazone. Indian J Chem 39A:1182–1186Google Scholar
- Wade PA (1992) Comprehensive organic synthesis. Pergamon Press, New York, Vol. 4, Ch. 4–10, p 1111Google Scholar