N-Hydroxy Derivatives: Key Organocatalysts for the Selective Free Radical Aerobic Oxidation of Organic Compounds

Ideas in Chemistry and Molecular Sciences: Advances in Synthetic Chemistry

Volumn , Issue , 2010, Pages 1-24

  Punta, Carlo ^a   Gambarotti, Cristian ^a  

^a POLITECNICO DI MILANO   (Italy)

Author keywords

2,2,6,6 tetramethylpiperidine 1 oxyl (TEMPO); N hydroxy derivatives; NHPI; NMBHA; Phthalimide N oxyl (PINO)

Indexed keywords

EID: 84885827482     PISSN: None     EISSN: None     Source Type: Book    
DOI: 10.1002/9783527630554.ch1     Document Type: Chapter

References (69)

1. Suresh, A.K., Sharma, M.M., and Sridhar, T.T. (2000) Engineering aspects of industrial liquid-phase air oxidation of hydrocarbons. Ind. Eng. Chem. Res., 39, 3958-3997.
2. Simandi, L.L. (1991) Dioxygen Activation and Homogeneous Catalytic Oxidation, Elsevier, Amsterdam
3. Parshall, G.W. and Ittel, S.D. (1992) Homogeneous Catalysis, 2nd edn, John Wiley & Sons, Inc., New York
4. Barton, D.H.R., Martell, A.E., and Sawyer, D.T. (1993) The Activation of Dioxygen and Homogeneous Catalytic Oxidation, Plenum, New York
5. Sheldon, R.A. and Kochi, J.K. (1981) Metal-catalysed Oxidations of Organic Compounds, Academic, New York.
6. Bäckvall, J.-E. (ed.) (2004) Modern Oxidation Methods, Wiley-VCH Verlag GmbH, Weinheim.
7. Centi, G., Trifirò, F., and Cavani, F. (2001) Selective Oxidation by Heterogeneous Catalysis, Kluwer Academic/ Plenum, New York
8. Sheldon, R.A. and van Bekkum, H. (2001) Fine Chemicals through Heterogeneous Catalysis, Wiley-VCH Verlag GmbH, Weinheim.
9. Zedda, A., Sala, M., and Schneider, A. (2002) Stable free nitroxyl radicals as oxidation catalysts and process for oxidation. WO02/058844
10. Baucherel, X. and Sheldon, R.A. (2002) Catalytic oxidation process. WO02/100810
11. Kühnle, A., Jost, C., Sheldon, R.A., Chatel, S., and Arends, I. (2003) Method for producing saturated alcohols, ketones, aldehydes and carboxylic acids. WO03/004447
12. Kühnle, A., Duda, M., Sheldon, R.A., Sasidharan, M., Arends, I., Schiffer, T., Fries, G., and Kirchhoff, J. (2001) Method for oxidizing hydrocarbons. WO01/74742.
13. Lucarini, M., Ferroni, F., Pedulli, G.F., Gardi, S., Lazzari, D., Schlingloff, G., and Sala, M. (2007) Metal free in situ formation of phthalimide N-oxyl radicals by light-induced homolysis of N-alkoxyphthalimides. Tetrahedron Lett., 48, 5331-5334.
14. Lucarini, M., Pedulli, G.F., and Cipollone, M. (1994) Bond dissociation enthalpy of α-tocopherol and other phenolic antioxidants. J. Org. Chem., 59, 5063-5070
15. Lucarini, M., Pedulli, G.F., Pedrielli, P., Cabiddu, S., and Fattuoni, C. (1996) Bond dissociation energies of O-H bonds in substituted phenols from equilibration studies. J. Org. Chem., 61, 9259-9263
16. Lucarini, M., Pedulli, G.F., Valgimigli, L., Amorati, R., and Minisci, F. (2001) Thermochemical and kinetic studies of a bisphenol antioxidant. J. Org. Chem., 66, 5456-5462
17. Brigati, G., Lucarini, M., Mugnaini, V., and Pedulli, G.F. (2002) Determination of the substituent effect on the O-H bond dissociation enthalpies of phenolic antioxidants by the EPR radical equilibration technique. J. Org. Chem., 67, 4828-4832.
18. Amorati, R.R., Lucarini, M.M., Mugnaini, V.V., Pedulli, G.F.G. F., Minisci, F.F., Fontana, F.F., Recupero, F.F., Astolfi, P.P., and Greci, L.L. (2003) Hydroxylamines as oxidation catalysts: thermochemical and kinetic studies. J. Org. Chem., 68, 1747-1754.
19. de Nooy, A.E.J., Besemer, A.C., and van Bekkum, H. (1996) On the use of stable organic nitroxyl radicals for the oxidation of primary and secondary alcohols. Synthesis, 10, 1153-1174.
20. Sheldon, R.A., Arends, I.W.C.E., Brink, G.J., and Dijksman, A. (2002) Green, catalytic oxidations of alcohols. Acc. Chem. Res., 35, 774-781
21. Dijksman, A., Arends, I.W.C.E., and Sheldon, R.A. (1999) Efficient ruthenium-TEMPO-catalysed aerobic oxidation of aliphatic alcohols into aldehydes and ketones. Chem. Commun., 1591, 1592
22. Dijksman, A., Arends, I.W.C.E., and Sheldon, R.A. (2001) The Ruthenium/TEMPO-catalysed aerobic oxidation of alcohols. Platinum Metals Rev., 45, 15
23. Dijksman, A., Marino-Gonzalez, A., Mairata I Payeras, A., Arends, I.W.C.E., and Sheldon, R.A. (2001) Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using Ruthenium/TEMPO as the catalytic system. J. Am. Chem. Soc., 123, 6826-6833.
24. Betzemeier, B.B., Cavazzini, M.M., Quici, S.S., and Knochel, P.P. (2000) Copper-catalysed aerobic oxidation of alcohols under fluorous biphasic conditions. Tetrahedron Lett., 41, 4343-4346.
25. Brink, G.J., Arends, I.W.C.E., and Sheldon, R.A. (2000) Green, catalytic oxidation of alcohols in water. Science, 287, 1636-1639.
26. Recupero, F. and Punta, C. (2007) Free radical functionalization of organic compounds catalysed by N-hydroxyphthalimide. Chem. Rev., 107, 3800-3842
27. Minisci, F., Punta, C., and Recupero, F. (2006) Mechanisms of the aerobic oxidations catalysed by N-hydroxyderivatives. Enthalpic, polar and solvent effects, "molecule-induced homolysis" and synthetic involvements. J. Mol. Catal. A Chem., 251, 129-149.
28. Ishii, Y., Sakaguchi, S., and Iwahama, T. (2001) Innovation of hydrocarbon oxidation with molecular oxygen and related reactions. Adv. Synth. Catal., 343, 393-427.
29. Fukuda, O., Sakaguchi, S., and Ishii, Y. (2001) A new strategy for catalytic Baeyer-Villiger oxidation of KA-oil with molecular oxygen using N-hydroxyphthalimide. Tetrahedron Lett., 42, 3479-3481
30. Aoki, Y., Hirai, N., Sakaguchi, S., and Ishii, Y. (2005) Aerobic oxidation of 1,3,5-triisopropylbenzene using N-hydroxyphthalimide (NHPI) as key catalyst. Tetrahedron, 61, 10995-10999
31. Foricher, J., Furbringer, C., and Pfoertner, K. (1986) Catalytic oxidation with N-hydroxydicarboxylic acid imides. EP Patent 0198351
32. Foricher, J., Furbringer, C., and Pfoertner, K. (1991) Process for the catalytic oxidation of isoprenoids having allylic groups. US Patent 5,030,739.
33. Minisci, F., Recupero, F., Punta, C., Gambarotti, C., Antonietti, F., Fontana, F.F., and Pedulli, G.F. (2002) A novel, selective free-radical carbamoylation of heteroaromatic bases by Ce(IV) oxidation of formamide, catalysed by N-hydroxyphthalimide. Chem. Commun., 2496-2497.
34. Einhorn, C., Einhorn, J., Marcadal, C., and Pierre, J.-L. (1997) Oxidation of organic substrates by molecular oxygen mediated by N-hydroxyphthalimide (NHPI) and acetaldehyde. Chem. Commun., 447-448.
35. Tong, X., Xu, J., and Miao, H. (2005) Highly efficient and metal-free aerobic hydrocarbons oxidation process by an o-phenanthroline-mediated organocatalytic system. Adv. Synth. Catal., 347, 1953-1957.
36. Baiocco, P., Barreca, A.M., Fabbrini, M., Galli, C., and Gentili, P. (2003) Promoting laccase activity towards non-phenolic substrates: a mechanistic investigation with some laccase- mediator systems. Org. Biomol. Chem., 1, 191-197
37. Astolfi, P., Brandi, P., Galli, C., Gentili, P., Gerini, M.F., Greci, L., and Lanzalunga, O. (2005) New mediators for the enzyme laccase: mechanistic features and selectivity in the oxidation of non-phenolic substrates. New J. Chem., 29, 1308-1317.
38. Sheldon, R.A. and Arends, I.W.C.E. (2004) Organocatalytic oxidations mediated by nitroxyl radicals. Adv. Synth. Catal., 346, 1051-1071.
39. Punta, C., Rector, C.L., and Porter, N.A. (2005) Peroxidation of polyunsaturated fatty acid methyl esters catalysed by N-methyl benzohydroxamic acid: a new and convenient method for selective synthesis of hydroperoxides and alcohols. Chem. Res. Toxicol., 18, 349-356.
40. Cecchetto, A., Fontana, F., Minisci, F., and Recupero, F. (2001) Efficient Mn- Cu and Mn- Co- TEMPO-catalysed oxidation of alcohols into aldehydes and ketones by oxygen under mild conditions. Tetrahedron Lett., 42, 6651-6653.
41. Minisci, F., Recupero, F., Cecchetto, A., Gambarotti, C., Punta, C., Faletti, R., Paganelli, R., and Pedulli, G.F. (2004) Mechanisms of the aerobic oxidation of alcohols to aldehydes and ketones, catalysed under mild conditions by persistent and non-persistent nitroxyl radicals and transition metal salts. polar, enthalpic, and captodative effects. Eur. J. Org. Chem., 1, 109-119.
42. Minisci, F., Fumagalli, C., and Pirola, R. (2001) Process for the preparation of carboxylic acids. WO01/58845A1.
43. Minisci, F., Recupero, F., Pedulli, G.F., and Lucarini, M. (2003) Transition metal salts catalysis in the aerobic oxidation of organic compounds: Thermochemical and kinetic aspects and new synthetic developments in the presence of N-hydroxy-derivative catalysts. J. Mol. Catal. A Chem., 204-205, 63-90
44. Minisci, F., Recupero, F., Fontana, F., Bjørsvik, H.R., and Liguori, L. (2002) Highly selective and efficient conversion of alkyl aryl and alkyl cyclopropyl ketones to aromatic and cyclopropane carboxylic acids by aerobic catalytic oxidation: a free-radical redox chain mechanism. Synlett, 610-612.
45. Benaglia, M., Puglisi, A., and Cozzi, F. (2003) Polymer-supported organic catalysts. Chem. Rev., 103, 3401
46. Cozzi, F. (2006) Immobilization of organic catalysts: when, why, and how. Adv. Synth. Catal., 348, 1367.
47. Fey, T., Fischer, H., Bachmann, S., Albert, K., and Bolm, C. (2001) Silica-supported TEMPO catalysts: synthesis and application in the Anelli oxidation of alcohols. J. Org. Chem., 66, 8154
48. Bolm, C. and Fey, T. (1999) TEMPO oxidations with a silica-supported catalyst. Chem. Commun., 1795
49. Verhoef, M.J., Peters, J.A., and van Bekkum, H. (1999) MCM-41 supported TEMPO as an environmentally friendly catalyst in alcohol oxidation. Stud. Surf. Sci. Catal., 125, 465-472
50. Ciriminna, R., Blum, J., Avnir, D., and Pagliaro, M. (2000) Sol- gel entrapped TEMPO for the selective oxidation of methyl α-D-glucopyranoside. Chem. Commun., 1441
51. Dijksman, A., Arends, I.W.C.E., and Sheldon, R.A. (2000) Polymer immobilised TEMPO (PIPO): an efficient catalyst for the chlorinated hydrocarbon solvent-free and bromide-free oxidation of alcohols with hypochlorite. Chem. Commun., 271.
52. Karimi, B., Biglari, A., Clark, J.H., and Budarin, V. (2007) Green, transition-metal-free aerobic oxidation of alcohols using a highly durable supported organocatalyst. Angew. Chem. Int. Ed., 46, 7210-7213.
53. 2 under mild conditions. Org. Process Res. Dev., 7, 794-798.
54. Minisci, F., Punta, C., Recupero, F., Fontana, F., and Pedulli, G.F. (2002) A new, highly selective synthesis of aromatic aldehydes by aerobic free-radical oxidation of benzylic alcohols, catalysed by N-hydroxyphthalimide under mild conditions. Polar and enthalpic effects. Chem. Commun., 688-689.
55. Annunziatini, C., Gerini, M.F., Lanzalunga, O., and Lucarini, M. (2004) Aerobic oxidation of benzyl alcohols catalysed by aryl substituted N-hydroxyphthalimides. Possible involvement of a charge-transfer complex. J. Org. Chem., 69, 3431-3438.
56. Minisci, F., Recupero, F., Punta, C., Guidarini, C., Fontana, F., and Pedulli, G.F. (2002) A new, highly selective, free-radical aerobic oxidation of silanes to silanols catalysed by N-hydroxyphthalimide under mild conditions. Synlett, 7, 1173-1175.
57. Minisci, F., Punta, C., Recupero, F., Fontana, F., and Pedulli, G.F. (2002) Aerobic oxidation of N-alkylamides catalysed by N-hydroxyphthalimide under mild conditions. Polar and enthalpic effects. J. Org. Chem., 67, 2671-2676.
58. Cecchetto, A., Minisci, F., Recupero, F., Fontana, F., and Pedulli, G.F. (2002) A new selective free radical synthesis of aromatic aldehydes by aerobic oxidation of tertiary benzylamines catalysed by N-hydroxyimides and Co(II) under mild conditions. Polar and enthalpic effects. Tetrahedron Lett., 43, 3605-3607.
59. Minisci, F., Recupero, F., Gambarotti, C., Punta, C., and Paganelli, R. (2003) Selective functionalisation of hydrocarbons by nitric acid and aerobic oxidation catalysed by N-hydroxyphthalimide and iodine under mild conditions. Tetrahedron Lett., 44, 6919-6922.
60. Minisci, F., Recupero, F., Cecchetto, A., Punta, C., Gambarotti, C., Fontana, F.F., and Pedulli, G.F. (2003) Polar effects in free-radical reactions. a nove1 homolytic acylation of heteroaromatic bases by aerobic oxidation of aldehydes, catalysed by N-hydroxyphthalimide and Co salts. J. Heterocycl. Chem., 40, 235-328.
61. Minisci, F., Recupero, F., Cecchetto, A., Gambarotti, C., Punta, C., Paganelli, R., Pedulli, G.F., and Fontana, F. (2004) Solvent and temperature effects in the free radical aerobic oxidation of alkyl and acyl aromatics catalysed by transition metal salts and N-hydroxyphthalimide: new processes for the synthesis of p-hydroxybenzoic acid, diphenols, and dienes for liquid crystals and cross-linked polymers. Org. Process Res. Dev., 8, 163-168.
62. Minisci, F., Porta, O., Recupero, F., Gambarotti, C., Paganelli, R., Pedulli, G.F., and Fontana, F. (2004) New free-radical halogenations of alkanes, catalysed by N-hydroxyphthalimide. Polar and enthalpic effects on the chemoand regio-selectivity. Tetrahedron Lett., 45, 1607-1609.
63. (2004) Daicel Chemical employs NHPI catalyst method for adipic acid. Focus Catal., 1, 7
64. Sawatari, N., Yokota, T., Sakaguchi, S., and Ishii, Y. (2001) Alkane oxidation with air catalysed by lipophilic N-hydroxyphthalimides without any solvent. J. Org. Chem., 66, 7889-7891
65. Baucherel, X., Gonsalvi, L., Arends, I.W.C.E., Ellwood, S., and Sheldon, R.A. (2004) Aerobic oxidation of cycloalkanes, alcohols and ethylbenzene catalysed by the novel carbon radical chain promoter NHS (N-hydroxysaccharin). Adv. Synth. Catal., 346, 286-296
66. Tong, X., Xu, J., and Miao, H. (2005) Highly efficient and metal-free aerobic hydrocarbons oxidation process by an o-phenanthroline-mediated organocatalytic system. Adv. Synth. Catal., 347, 1953-1957.
67. Minisci, F., Gambarotti, C., Pierini, M., Porta, O., Punta, C., Recupero, F., Lucarini, M., and Mugnaini, V. (2006) Molecule-induced homolysis of N-hydroxyphthalimide (NHPI) by peracids and dioxirane. A new, simple, selective aerobic radical epoxidation of alkenes. Tetrahedron Lett., 47, 1421-1424
68. Punta, C., Moscatelli, D., Porta, O., Minisci, F., Gambarotti, C., and Lucarini, M. (2008) Selective aerobic radical epoxidation of α-olefins catalysed by N-hydroxyphthalimide, in Mechanisms in Homogeneous and Heterogeneous Epoxidation Catalysis (ed. S.T.Oyama), Elsevier, pp. 217-229.
69. Minisci, F., Porta, O., Punta, C., Recupero, F., Gambarotti, C., and Pierini, M. (2008) Process for the preparation of phenol by means of new catalytic systems. WO2008037435A1.