First Sustainable Aziridination of Olefins Using Recyclable Copper-Immobilized Magnetic Nanoparticles

Abstract

The first copper-catalyzed aziridination of olefins using re­cyclable magnetic nanoparticles is described. Magnetic nanoparticles were modified with dopamine and used as a support to coordinate copper. The methodology was optimized with styrene as olefin and using [N-(p-toluenesulfonyl)imino]phenyliodinane (PhI=NTs) as nitrene source. A microwave irradiation decreased the reaction time by 4-fold compared to conventional heating method. The catalyst was recovered by simple magnetic extraction and could be reused successfully up to five times without significant loss of activity. The methodology was ­applied to a range of different olefins leading to moderate to excellent yields in the formation of the expected aziridine.

Key words

sustainable aziridination - magnetic nanoparticle - copper catalyst - nitrene insertion

• References and Notes

• 1 For a general review about aziridine see: Sweeney JB. Chem. Soc. Rev. 2002; 31: 247
• 2 For general review about C–H amination and aziridination, see: Dauban P, Dodd RH. In Amino Group Chemistry: From Synthesis to the Life Sciences . Ricci A. Wiley-VCH; Weinheim: 2008: 55
• 3 Compain P, Toumieux S. In Targets in Heterocyclic Systems. Attanasi OA, Spinelli D. Italian Society of Chemistry; Rome: 2007: 338
• 4 Watson ID. G, Yu L, Yudin AK. Acc. Chem. Res. 2006; 39: 194
• 5 Li AH, Dai LX, Aggarwal VK. Chem. Rev. 1997; 97: 2341
• 6 Ismail FM. D, Levitsky DO, Dembitsky VM. Eur. J. Med. Chem. 2009; 414: 3373
• 7 Chang YJ, Hsuan YC, Ying Lai AC, Chiann Han Y, Hou DR. Org. Lett. 2016; 18: 808
• 8 Hsueh N, Clarkson GJ, Shipman M. Org. Lett. 2015; 17: 3632
• 9 Lwowski W. In Carbonylnitrenes in Nitrenes . Lwowski W. Interscience Publishers; New York: 1970: 185
• 10 Lwowski W. In Acyl Azides and Nitrenes . In Azides and Nitrenes, Reactivity and Utility . Scriven FV. Academic Press; New York: 1984: 205
• 11 Degennaro L, Trinchera P, Luisi R. Chem. Rev. 2014; 114: 7881
• 12 Chanda BM, Vyas R, Bedekar AV. J. Org. Chem. 2001; 66: 30
• 13 Halfen JA. Curr. Org. Chem. 2005; 9: 657
• 14 Evans DA, Faul MM, Bilodeau MT, Anderson BA, Barnes DM. J. Am. Chem. Soc. 1993; 115: 5328
• 15 Müller P, Fruit C. Chem. Rev. 2003; 103: 2905
• 16 Dauban P, Sanière L, Tarrade A, Dodd RH. J. Am. Chem. Soc. 2001; 123: 7707
• 17 Bazarganipour M, Salavati-Niasari M. Appl. Catal., A 2015; 502: 57
• 18 Jeffs L, Arquier D, Kariuki B, Bethell D, Bulman Page PC, Hutchings GJ. Org. Biomol. Chem. 2011; 9: 1079
• 19 Traa Y, Murphy DM, Farley RD, Hutchings GJ. Phys. Chem. Chem. Phys. 2001; 3: 1073
• 20 Gullick J, Taylor S, McMorna P, Bethell D, Bulman Page PC, Hancock FE, King F, Hutchings G. J. Mol. Catal. A: Chem. 2002; 180: 85
• 21 Kantam ML, Jaya VS, Lakshmi MJ, Reddy BR, Choudary BM, Bhargava SK. Catal. Commun. 2007; 8: 1963
• 22 Pereira C, Biernacki K, Rebelo SL. H, Magalhães AL, Carvalho AP, Piresb J, Freire C. J. Mol. Catal. A: Chem. 2009; 312: 53
• 23 Shultz MD, Reveles JU, Khanna SN, Carpenter EE. J. Am. Chem. Soc. 2007; 129: 2482
• 24 Rathore PS, Patidar R, Thakore S. RSC Adv. 2014; 4: 41111
• 25 Long Y, Liang K, Niu J, Tong X, Yuan B, Ma J. New J. Chem. 2015; 39: 2988
• 26 Guin D, Baruwati B, Manorama SV. Org. Lett. 2007; 9: 1419
• 27 Polshettiwar V, Varma RS. Org. Biomol. Chem. 2009; 7: 37
• 28 Kolotilov SV, Shvets O, Cador O, Kasian N, Pavlov VG, Ouahab A, Ilyin VG, Pavlishchuk VV. J. Solid State Chem. 2006; 179: 2426
• 29 Mansuy D, Mahy J.-P, Dureault A, Bedi G, Battioni P. J. Chem. Soc., Chem. Commun. 1984; 1161
• 30 Nasir Baig RB, Varma RS. Chem. Commun. 2012; 48: 2582
• 31 Appukkuttan P, Van der Eycken E. Eur. J. Org. Chem. 2008; 1133
• 32 Brandt P, Södergren MJ, Andersson PG, Norrby PO. J. Am. Chem. Soc. 2000; 122: 8013
• 33 General Synthetic Procedure for Aziridination To a mixture of olefin substrates (0.4 mmol), 10% Fe₃O₄-Dopa-Cu catalyst (0.04 mmol, 0.1 equiv.) in dry acetonitrile was added PhI=NTs (0.48 mmol, 1.2 equiv.) portionwise in 5 times in microwave at 70 °C under argon atmosphere, and the whole mixture was stirred until TLC showed a complete conversion (10 min to 3 h). The catalyst was removed with an external magnet and washed with dried MeCN. The solvent was removed under reduce pressure. The crude was purified by flash chromatography on silica gel using a Reveleris™ Flash System.