Synlett 2014; 25(20): 2923-2927
DOI: 10.1055/s-0034-1378913
letter
© Georg Thieme Verlag Stuttgart · New York

TEMPO/NBu4Br-Catalyzed Selective Alcohol Oxidation with Periodic Acid

Mariam Attoui
Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), UMR 5246 CNRS, Equipe SURCOOF, bât. Raulin, 43, Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France   Fax: +33(4)72431214   Email: vatele@univ-lyon1.fr
,
Jean-Michel Vatèle*
Université Lyon 1, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires (ICBMS), UMR 5246 CNRS, Equipe SURCOOF, bât. Raulin, 43, Bd du 11 Novembre 1918, 69622 Villeurbanne Cedex, France   Fax: +33(4)72431214   Email: vatele@univ-lyon1.fr
› Author Affiliations
Further Information

Publication History

Received: 15 September 2014

Accepted: 02 October 2014

Publication Date:
29 October 2014 (eFirst)

Abstract

Oxidation of primary and secondary alcohols, using catalytic amounts of TEMPO and tetra-n-butylammonium bromide in combination with periodic acid and wet alumina in dichloromethane is described. This oxidizing system is compatible with a broad range of functional groups and acid-sensitive protecting groups. Chemoselective oxidation of secondary alcohols in the presence of primary alcohols was observed.

 
  • References and Notes

    • 3a Fatiadi AJ. Synthesis 1976; 65
    • 3b Fatiadi AJ. Synthesis 1976; 133
    • 3c Fatiadi AJ. Synthesis 1987; 85
    • 4a Mancuso AJ, Swern D. Synthesis 1981; 165
    • 4b Tidwell TT. Synthesis 1990; 857
    • 4c Tidwell TT. Org. React. 1990; 39: 297
  • 5 For a recent review, see: Tohma H, Kita Y. Adv. Synth. Catal. 2004; 346: 111
  • 6 Dess DB, Martin JC. J. Org. Chem. 1983; 48: 4155
  • 7 Frigerio M, Santagostino M, Sputore S, Palmisano G. J. Org. Chem. 1995; 60: 7272

    • For reviews of TEMPO-catalyzed alcohol oxidation, see:
    • 8a Bobbitt JM, Flores MC. L. Heterocycles 1988; 27: 509
    • 8b Yamaguchi M, Miyazawa T, Takata T, Endo T. Pure Appl. Chem. 1990; 62: 217
    • 8c de Nooy AE. J, Besemer AC, Van Bekkum HV. Synthesis 1996; 1153
    • 8d Adam W, Saha-Möller CR, Ganseshpure PA. Chem. Rev. 2001; 3499
    • 8e Sheldon RA, Arends IW. C. E, Ten Brink G.-J, Dijksman A. Acc. Chem. Res. 2002; 35: 774
    • 8f Bobbitt JM, Brückner C, Merbouh N. Org. React. 2010; 74: 103

      Halogen-based reagents. For X2, see:
    • 9a Miyazama T, Endo T, Shiihashi S, Okawara M. J. Org. Chem. 1985; 50: 1332
    • 9b Bjørsvih H.-R, Liguori L, Costantino F, Minisci F. Org. Process Res. Dev. 2002; 6: 197
    • 9c Miller RA, Hoerrner RS. Org. Lett. 2003; 5: 285
    • 9d Liu R, Liang X, Dong C, Hu X. J. Am. Chem. Soc. 2004; 126: 4112

    • Bleach:
    • 9e Anelli PL, Biffi C, Montanari F, Quici S. J. Org. Chem. 1987; 52: 2559
    • 9f Anelli PL, Banfi S, Montanari F, Quici S. J. Org. Chem. 1989; 54: 2970
    • 9g Siedlecka R, Skarzewski J, Mlochowski J. Tetrahedron Lett. 1990; 31: 2177
    • 9h Bolm C, Fey T. Chem. Commun. 1999; 1795
    • 9i Dijksman A, Arends IW. C. E, Sheldon RA. Chem. Commun. 2000; 271

    • NCS:
    • 9j Einhorn J, Einhorn C, Ratajczak F, Pierre J.-L. J. Org. Chem. 1996; 61: 7452

    • NaBrO2:
    • 9k Inokuchi T, Matsumoto S, Nishiyama T, Torii S. J. Org. Chem. 1990; 55: 462

    • NaClO2:
    • 9l Zhao M, Li J, Mano E, Song Z, Tschaen DM, Grabowski EJ. J, Reider PJ. J. Org. Chem. 1999; 64: 2564

    • Trichloroisocyanuric acid:
    • 9m De Luca L, Giacomelli G, Porcheddu A. Org. Lett. 2001; 3: 3041
    • 9n De Lucca L, Giacomelli G, Masala S, Porcheddu A. J. Org. Chem. 2003; 68: 4999

      Examples of other reoxidants for TEMPO. For MCPBA, see:
    • 10a Cella JA, Kelley JA, Kenhan EF. J. Org. Chem. 1975; 40: 1860
    • 10b Ganem B. J. Org. Chem. 1975; 40: 1998

    • Oxone:
    • 10c Rychnovski SD, Vaidyanathan R. J. Org. Chem. 1999; 64: 310
    • 10d Bolm C, Magnus AS, Hildebrand JP. Org. Lett. 2000; 2: 1173
    • 11a De Mico A, Margarita R, Parlanti L, Vescovi A, Piancatelli G. J. Org. Chem. 1997; 62: 6974
    • 11b Epp JB, Widlanski TS. J. Org. Chem. 1999; 64: 293
    • 11c Sakuratani K, Togo H. Synthesis 2003; 21
    • 11d Van Der Bos LJ, Litjens RE. J. N, Van den Berg RJ. B. H. N, Overkleeft HS, Van der Marel GA. Org. Lett. 2005; 7: 2007
  • 12 Vatèle J.-M. Synlett 2014; 25: 115
    • 13a Vatèle J.-M. Tetrahedron Lett. 2006; 47: 715
    • 13b Vatèle J.-M. Synlett 2006; 2055
    • 13c Vatèle J.-M. Synlett 2008; 1785
    • 13d Vatèle J.-M. Synlett 2009; 2143
    • 13e Vatèle J.-M. Tetrahedron 2010; 66: 904
    • 13f Barnych B, Vatèle J.-M. Synlett 2011; 2048
    • 13g Vatèle J.-M. Synlett 2014; 25: 1275
  • 14 Lei M, Hu R.-J, Wang Y.-G. Tetrahedron 2006; 62: 8928
  • 15 Kim SS, Nehru C. Synlett 2002; 616

    • For examples of wet alumina mediated oxidations, see:
    • 16a Hirano M, Oose M, Morimoto T. Bull. Chem. Soc. Jpn. 1991; 64: 1046
    • 16b Hirano M, Oose M, Morimoto T. Chem. Lett. 1991; 331
    • 16c Greenhalgh RP. Synlett 1992; 235
    • 16d Ceccherelli P, Curini M, Marcotullio MC, Epifano F, Rosati O. Synlett 1996; 767
  • 17 For a study on the mechanism of Al2O3-catalyzed oxidation, see: Kropp PJ, Breton GW, Fields JD, Tung JC, Loomis BR. J. Am. Chem. Soc. 2000; 122: 4280
  • 18 Alcohol oxidation with periodic acid and catalytic bromide anion has been described: Zolfigol MA, Shirini F, Chehardoli G, Kolvari E. J. Mol. Catal. A: Chem. 2007; 265: 272
  • 19 Appropriate physical and analytical data were obtained for all new compounds.
  • 20 Typical Procedure for the Oxidation of Alcohols (Table 2, Entry 21) Wet alumina was prepared by mixing neutral alumina (50 g, Fluka ref 06300; Brockmann activity 1) with H2O (10 g) and shaking until a free-flowing homogeneous powder was obtained. To a solution of 3-methylhexane-1,3-diol (20a, 0.132 g, 1 mmol) in CH2Cl2 (3 mL) were successively added TEMPO (7.8 mg, 5 mol%), wet alumina (0.913 g), TBAB (16 mg, 5 mol%), and H5IO6 (0.274 g, 1.2 equiv). The brownish suspension was stirred for 5 h at r.t., filtered, and the filtrate was washed with sat. Na2S2O3 aq solution, dried (Na2SO4), and concentrated in vacuo. The residue was purified by chromatography on silica gel (PE–Et2O, 1:2) to give the hydroxyaldehyde 20b as a liquid (94 mg, 72%). 1H NMR (300 MHz, C6D6): δ = 9.57 (t, J = 2.3 Hz, 1 H), 2.43 (s, 1 H), 2.14 (dd, J = 15.8, 2.4 Hz, 1 H), 2.04 (dd, J = 15.8, 2.4 Hz, 1 H), 1.32–1.09 (m, 4 H), 1.02 (s, 3 H), 0.8 (t, J = 7.1 Hz, 3 H). 13C NMR (75 MHz, C6D6): δ = 202.6, 71.5, 54.2, 45.3, 27.3, 17.3, 14.6. ESI-HRMS: m/z [M – H] calcd for C7H13O2: 129.0916; found: 129.0918.
    • 21a Shibuya M, Tomizawa M, Suzuki I, Iwabuchi Y. J. Am. Chem. Soc. 2006; 128: 8412
    • 21b Lauber MB, Stahl SS. ACS Catal. 2013; 3: 2612
    • 21c Holan M, Jahn U. Org. Lett. 2014; 16: 58
  • 22 For a review on AZADO and its derivatives, see: Iwabuchi Y. Chem. Pharm. Bull. 2013; 61: 1197
    • 23a Anderson JC, McDermott BP, Griffin EJ. Tetrahedron 2000; 56: 8747
    • 23b Avi M, Gaisberger R, Feichtenhofer S, Griengl H. Tetrahedron 2009; 65: 5418
    • 24a Semmelhack MF, Chou CS, Cortes DA. J. Am. Chem. Soc. 1983; 105: 4492
    • 24b Semmelhack MF, Schmid CR, Cortes DA, Chou CS. J. Am. Chem. Soc. 1984; 106: 3374
    • 24c Shibuya M, Tomizawa M, Sasano Y, Iwabuchi Y. J. Org. Chem. 2009; 74: 4619
    • 24d Hoover JM, Stahl SS. J. Am. Chem. Soc. 2011; 133: 16901
  • 25 Zhao X.-F, Zhang C. Synthesis 2007; 551
  • 26 For a review on the chemoselective oxidation of secondary alcohols, see: Arterburn JB. Tetrahedron 2001; 57: 9765
  • 27 Bailey WF, Bobbitt JM, Wiberg KB. J. Org. Chem. 2007; 72: 4504