A simple one-pot procedure for the preparation of imines from the corresponding aldehydes and amines, and their subsequent oxidation reaction with m -CPBA to produce synthetically useful oxaziridines is reported. The method is applicable to imines derived from both aliphatic and aromatic aldehydes and diverse alkyl amines. Short reaction times, essentially quantitative yields, very mild reaction conditions, and easy purification are the main features of the procedure reported herein.
Toda, F. (2001) Development of Solvent-Free Organic Synthetic Method. Fine Chemical, 30, 5-15.
Wang, G.-W. (2013) Mechanochemical Organic Synthesis. Chemical Society Reviews, 42, 7668-7700. https://doi.org/10.1039/c3cs35526h
Hernández, J.G., Avila-Ortiz, C.G. and Juaristi, E. (2014) Useful Chemical Activation Alternatives in Solvent-Free Organic Reactions. In: Knochel, P. and Molander, G.A., Eds., Comprehensive Organic Synthesis, 2nd Edition, Elsevier, B.V., Amsterdam, 287-314. https://doi.org/10.1016/B978-0-08-097742-3.00935-6
Perin, G., Alves, D., Jacob, R.G., Barcellos, A.M., Soares, L.K. and Lenardao, E.J. (2016) Synthesis of Organochalcogen Compounds Using Non-Conventional Reaction Media. ChemistrySelect, 1, 205-258. https://doi.org/10.1002/slct.201500031
Do, J.-L. and Friscic, T. (2017) Chemistry 2.0: Developing a New, Solvent-Free System of Chemical Synthesis Based on Mechanochemistry. Synlett, 28, 2066-2092. https://doi.org/10.1055/s-0036-1590854
Loupy, A., Petit, A., Hamelin, J., Texier-Boullet, F., Jacquault, P. and Mathe, D. (1998) New Solvent-Free Organic Synthesis Using Focused Microwaves. Synthesis, 29, 1213-1234.
Koshima, H. (2005) Microwave-Assisted Solvent-Free Organic Synthesis. Fine Chemical, 34, 27-32.
Serpone, N. and Colarusso, P. (1994) Sonochemistry: I. Effects of Ultrasound on Heterogeneous Chemical Reactions—A Useful Tool to Generate Radicals and to Examine Reaction Mechanisms. Research on Chemical Intermediates, 20, 635-679. https://doi.org/10.1163/156856794X00261
Varma, R.S. (2007) “Greener” Chemical Syntheses Using Mechanochemical Mixing or Microwave and Ultrasound Irradiation. Green Chemistry Letters and Reviews, 1, 37-45. https://doi.org/10.1080/17518250701756991
Calvino-Casilda, V. (2014) Progress in Solvent-Free Sonochemical Assisted Synthesis of Fine and Specialty Chemicals. In: Luque, R., Ed., Green Chemistry, Nova Science, Hauppauge, New York, 107-126.
Lupacchini, M., Mascitti, A., Giachi, G., Tonucci, L., d’Alessandro, N., Martinez, J. and Colacino, E. (2017) Sonochemistry in Non-Conventional, Green Solvents or Solvent-Free Reactions. Tetrahedron, 73, 609-653. https://doi.org/10.1016/j.tet.2016.12.014
Tanaka, K. and Toda, F. (2000) Solvent-Free Organic Synthesis. Chemical Reviews, 100, 1025-1074. https://doi.org/10.1021/cr940089p
Nagendrappa, G. (2002) Organic Synthesis under Solvent-Free Condition: An Environmentally Benign Procedure I. Resonance, 7, 59-63. https://doi.org/10.1007/BF02835544
Nagendrappa, G. (2002) Organic Synthesis under Solvent-Free Condition: An Environmentally Benign Procedure II. Resonance, 7, 64-69. https://doi.org/10.1007/BF02868200
Ramamurthy, V. and Sivaguru, J. (2016) Supramolecular Photochemistry as a Potential Synthetic Tool: Photocycloaddition. Chemical Reviews, 116, 9914-9993. https://doi.org/10.1021/acs.chemrev.6b00040
Kobayashi, S., Mori, Y., Fossey, J.S. and Salter, M.M. (2011) Catalytic Enantioselective Formation of C-C Bonds by Addition to Imines and Hydrazones: A Ten-Year Update. Chemical Reviews, 111, 2626-2704. https://doi.org/10.1021/cr100204f
Charette, A.B. (2010) Stereoselective Synthesis of α-Branched Amines by Nucleophilic Addition of Unstabilized Carbanions to Imines. In: Nugent, T.C., Ed., Chiral Amine Synthesis, Wiley VCH, Weinheim, 1-49. https://doi.org/10.1002/9783527629541.ch1
Cogan, D.A. and Ellman, J.A. (1999) Asymmetric Synthesis of α,α-Dibranched Amines by the Trimethylaluminum-Mediated 1,2-Addition of Organolithiums to tert-Butanesulfinyl Ketimines. Journal of the American Chemical Society, 121, 268-269. https://doi.org/10.1021/ja983217q
Liu, G., Cogan, D.A., Owens, T.D., Tang, T.P. and Ellman, J.A. (1999) Synthesis of Enantiomerically Pure N-tert-Butanesulfinyl Imines (tert-Butanesulfinimines) by the Direct Condensation of tert-Butanesulfinamide with Aldehydes and Ketones. The Journal of Organic Chemistry, 64, 1278-1284. https://doi.org/10.1021/jo982059i
Mukade, T., Dragoli, D.R. and Ellman, J.A. (2003) Parallel Solution-Phase Asymmetric Synthesis of α-Branched Amines. Journal of Combinatorial Chemistry, 5, 590-596. https://doi.org/10.1021/cc030016w
Morales, S., Guijarro, F.G., García Ruano, J.L. and Cid, M.B. (2014) A General Aminocatalytic Method for the Synthesis of Aldimines. Journal of the American Chemical Society, 136, 1082-1089. https://doi.org/10.1021/ja4111418
Reeves, J.T., Visco, M.D., Marsini, M.A., Grinberg, N., Busacca, C.A., Mattson, A.E. and Senanayake, C.H. (2015) A General Method for Imine Formation Using B(OCH2CF3)3. Organic Letters, 17, 2442-2445. https://doi.org/10.1021/acs.orglett.5b00949
García Ruano, J.L., Alemán, J., Fajardo, C. and Parra, A. (2005) A New General Method for the Preparation of N-Sulfonyloxaziridines. Organic Letters, 7, 5493-5496. https://doi.org/10.1021/ol052250w
Jang, G.S., Lee, J., Seo, J. and Woo, S.K. (2017) Synthesis of 4-Isoxazolines via Visible-Light Photoredox-Catalyzed [3 + 2] Cycloaddition of Oxaziridines with Alkynes. Organic Letters, 19, 6448-6451. https://doi.org/10.1021/acs.orglett.7b03369
Zhang, G. and Hanson, S.K. (2013) Cobalt-Catalyzed Acceptorless Alcohol Dehydrogenation: Synthesis of Imines from Alcohols and Amines. Organic Letters, 15, 650-653. https://doi.org/10.1021/ol303479f
Esteruelas, M.A., Honczek, N., Oliván, M., Oñate, E. and Valencia, M. (2011) Direct Access to POP-Type Osmium(II) and Osmium(IV) Complexes: Osmium a Promising Alternative to Ruthenium for the Synthesis of Imines from Alcohols and Amines. Organometallics, 30, 2468-2471. https://doi.org/10.1021/om200290u
Xu, C., Goh, L.Y. and Pullarkat, S. (2011) Efficient Iridium-Thioether-Dithiolate Catalyst for β-Alkylation of Alcohols and Selective Imine Formation via N-Alkylation Reactions. Organometallics, 30, 6499-6502. https://doi.org/10.1021/om200883e
Zhang, E., Tian, H., Xu, S., Yu, X. and Xu, Q. (2013) Iron-Catalyzed Direct Synthesis of Imines from Amines or Alcohols and Amines via Aerobic Oxidative Reactions under Air. Organic Letters, 15, 2704-2707. https://doi.org/10.1021/ol4010118
Chen, B., Wang, L. and Gao, S. (2015) Recent Advances in Aerobic Oxidation of Alcohols and Amines to Imines. ACS Catalysis, 5, 5851-5876. https://doi.org/10.1021/acscatal.5b01479
Davis, F.A., Lamendola Jr., J., Nadir, U., Kluger, E.W., Sedergran, T.C., Panunto, T.W., Billmers, R., Jenkins Jr., R., Turchi, I.J., Watson, W.H., Chen, J.S. and Kimuralb, M. (1980) Chemistry of Oxaziridines. 1. Synthesis and Structure of 2-Arenesulfonyl-3-Aryloxaziridines. A New Class of Oxaziridines. Journal of the American Chemical Society, 102, 2000-2005. https://doi.org/10.1021/ja00526a040
Davis, F.A. and Stringer, O.D. (1982) Chemistry of Oxaziridines. 2. Improved Synthesis of 2-Sulfonyloxaziridines. Journal of Organic Chemistry, 47, 1774-1775. https://doi.org/10.1021/jo00348a039
Davis, F.A., Chattopadhyay, S., Towson, J.C., Lal, S. and Reddy, T. (1988) Chemistry of Oxaziridines. 9. Synthesis of 2-Sulfonyl- and 2-Sulfamyloxaziridines Using Potassium Peroxymonosulfate (Oxone). Journal of Organic Chemistry, 53, 2087-2089. https://doi.org/10.1021/jo00244a043
Collados, J.F., Toledano, E., Guijarro, D. and Yus, M. (2012) Microwave-Assisted Solvent-Free Synthesis of Enantiomerically Pure N-(tert-Butylsulfinyl) Imines. Journal of Organic Chemistry, 77, 5744-5750. https://doi.org/10.1021/jo300919x
Suzuki, S., Sakaki, S., Ishizuka, S., Nishino, T., Ito, H., Nonaka, R., Noike, M., Kodama, T., Nozaka, H., Sato, T., Agematsu, H., Maruyama, K., Oyamada, S., Kuroishi, T., Sasaki, K., Yagawa, K., Yoshioka, M. and Yokoyama, Y. (2018) Efficient Solvent- and Catalyst-Free Syntheses of Imine Derivatives Applying the Pressure Reduction Technique: Remarkable Change of the Reaction Rate with the Phase Transition. Green and Sustainable Chemistry, 8, 167-179.
Williamson, K.S., Michaelis, D.J. and Yoon, T.P. (2014) Advances in the Chemistry of Oxaziridines. Chemical Reviews, 114, 8016-8036. https://doi.org/10.1021/cr400611n
Vidal, J., Drouin, J. and Collet, A. (1991) N-Amination Using N-Methoxycarbonyl-3-Phenyloxaziridine. Direct Access to Chiral N-β-Protected α-Hydrazinoacids and Carbazates. Journal of the Chemical Society, Chemical. Communications, No. 6, 435-437. https://doi.org/10.1039/C39910000435
Vidal, J., Guy, L., Sterin, S. and Collet, A. (1993) Electrophilic Amination: Preparation and Use of N-Boc-3-(4-Cyanophenyl)Oxaziridine, a New Reagent That Transfers a N-Boc Group to N- and C-Nucleophiles. Journal of Organic Chemistry, 58, 4791-4793. https://doi.org/10.1021/jo00070a007
Emmons, W.D. (1957) The Preparation and Properties of Oxaziranes. Journal of the American Chemical Society, 79, 5739-5754. https://doi.org/10.1021/ja01578a043
Minisci, F., Galli, R., Malatesta, V. and Caronna, T. (1970) Nucleophilic Character of Alkyl Radicals—II: Selective Alkylation of Pyridine, Quinoline and Acridine by Hydroperoxides and Oxaziranes. Tetrahedron, 26, 4083-4091. https://doi.org/10.1016/S0040-4020(01)93049-2
Leung, C.H., Voutchkova, A.M., Crabtree, R.H., Balcells, D. and Eisenstein, O. (2007) Atom Economic Synthesis of Amides via Transition Metal Catalyzed Rearrangement of Oxaziridines. Green Chemistry, 9, 976-979. https://doi.org/10.1039/b706164a
Zhao, E., Zhou, F. and Zhao, Y. (2019) Lewis Acids Promoted [3 + 2] Cycloaddition of Oxaziridines and Cyclic Allylic Alcohols through Carbonyl Imine Intermediates. Journal of Organic Chemistry, 84, 4282-4293. https://doi.org/10.1021/acs.joc.9b00246
Fabio, M., Ronzini, L. and Troisi, L. (2007) Synthesis of New 3,5-Diarylisoxazolidines by Cycloaddition of Oxaziridines and Alkenes. Tetrahedron, 63, 12896-12902. https://doi.org/10.1016/j.tet.2007.10.044
Fabio, M., Ronzini, L. and Troisi, L. (2008) Synthesis of Stable Isoxazolines by [3+2] Cycloaddition of Oxaziridines with Alkynes. Tetrahedron, 64, 4979-4984. https://doi.org/10.1016/j.tet.2008.03.092
Michaelis, D.J., Shaffer, C.J. and Yoon, T.P. (2007) Copper(II)-Catalyzed Aminohydroxylation of Olefins. Journal of the American Chemical Society, 129, 1866-1867. https://doi.org/10.1021/ja067894t
Michaelis, D.J., Williamson, K.S. and Yoon, T.P. (2009) Oxaziridine-Mediated Enantioselective Aminohydroxylation of Styrenes Catalyzed by Copper(II) Bis(Oxazoline) Complexes. Tetrahedron, 65, 5118-5124. https://doi.org/10.1016/j.tet.2009.03.012
DesMarteau, D.D., Petrov, V.A., Montanari, V., Pregnolato, M. and Resnati, G. (1994) Mild and Selective Oxygenation of Sulfides to Sulfoxides and Sulfones by Perfluoro-cis-2,3-Dialkyloxaziridines. Journal of Organic Chemistry, 59, 2762-2765. https://doi.org/10.1021/jo00089a020
Bohé, L., Luscinchi, M. and Luscinchi, X. (1999) Oxygen Atom Transfer from a Chiral N-Alkyl Oxaziridine Promoted by Acid. The Asymmetric Oxidation of Sulfides to Sulfoxides. Tetrahedron, 55, 155-166. https://doi.org/10.1016/S0040-4020(98)01035-7
Schoumacker, S., Hamelin, O., Téti, S., Pécaut, J. and Fontecave, M. (2005) Activation of Oxaziridines by Lewis Acids: Application in Enantioselective Sulfoxidation. Journal of Organic Chemistry, 70, 301-308. https://doi.org/10.1021/jo048380k
Widmer, J. and Keller-Schierlein, W. (1974) Stoffwechselprodukte von Mikroorganismen. 130. Mitteilung. Synthese des δ-N-Hydroxy-L-Arginins. Helvetica Chimica Acta, 57, 657-664. https://doi.org/10.1002/hlca.19740570318
Kraïem, J., Othman, R.B. and Hassine, B.B. (2004) Synthesis of Oxaziridines by Oxidation of Imines with the Trichloroacetonitrile–Hydrogen Peroxide System. Comptes Rendus Chimie, 7, 1119-1126. https://doi.org/10.1016/j.crci.2003.12.002
Kitagawa, S., Moru, H., Odagiri, T., Suzuki, K., Kikkawa, Y., Osugi, R. and Kirihara, M. (2019) A Concise, Catalyst-Free Synthesis of Davis’ Oxaziridines Using Sodium Hypochlorite. SynOpen, 3, 21-25.
Suda, K., Hino, F. and Yijima, C. (1986) Mechanism of Base-Promoted Eliminative Fragmentations of 2-Alkyl-3-Phenyloxaziridines. Journal of Organic Chemistry, 51, 4232-4239. https://doi.org/10.1021/jo00372a024
Komatsu, M., Ohgishi, H., Ohshiro, Y. and Agawa, T. (1976) Reaction of Enamine with Oxaziridine or Schiff Base Facile Preparation of Substituted Pyridine. Tetrahedron Letters, 17, 4589-4592. https://doi.org/10.1016/S0040-4039(00)93939-X