2
177 Dakin oxidation Oxidation of aryl aldehydes or aryl ketones to phenols using basic hydrogen per- oxide conditions. Cf. Baeyer–Villiger oxidation. HO CHO H 2 O 2 , NaOH 45 50 o C HO OH HCO 2 H O O H HO H O HO O H O HO aryl migration O HO H OH O hydrolysis HO O H O OH HO 2 CH HO OH HO O CHO 2 Example 1 6 OBn CHO NHCO 2 t-Bu CO 2 H 2.5 eq. 30% H 2 O 2 4% (PhSe) 2 , CH 2 Cl 2 , 18 h OBn O NHCO 2 t-Bu CO 2 H CHO NH 3 , MeOH, 1 h 78% OBn OH NHCO 2 t-Bu CO 2 H

Dakin Oxidation

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  • 177

    Dakin oxidation

    Oxidation of aryl aldehydes or aryl ketones to phenols using basic hydrogen per-oxide conditions. Cf. BaeyerVilliger oxidation.

    HO CHOH2O2, NaOH

    4550 oCHO OH HCO2H

    O O H

    HOH

    OHO

    OH

    O

    HO

    aryl

    migration

    OHO

    H OHOhydrolysisHO O

    HO

    OH

    HO2CH HO OHHO O CHO2

    Example 16

    OBnCHO

    NHCO2t-Bu

    CO2H

    2.5 eq. 30% H2O2

    4% (PhSe)2, CH2Cl2, 18 h

    OBnO

    NHCO2t-Bu

    CO2H

    CHONH3, MeOH, 1 h

    78%

    OBnOH

    NHCO2t-Bu

    CO2H

  • 178

    Example 27

    HO

    CHO urea-hydrogen peroxide (UHP)

    solvent-free, 55 oC, 3 h, 83% HO

    OH

    References:

    1. Dakin, H. D. J. Am. Chem. Soc. 1909, 42, 477. Henry D. Dakin (18801952) was born in London, England. During WWI, he invented his hypochlorite solution (Da-kins solution), which became a popular antiseptic for the treatment of wounds. After the Great War, he emmigrated to New York, where he investigated the B vitamins.

    2. Hocking, M. B.; Bhandari, K.; Shell, B.; Smyth, T. A. J. Org. Chem. 1982, 47, 4208. 3. Matsumoto, M.; Kobayashi, H.; Hotta, Y. J. Org. Chem. 1984, 49, 4740. 4. Zhu, J.; Beugelmans, R.; Bigot, A.; Singh, G. P.; Bois-Choussy, M. Tetrahedron Lett.

    1993, 34, 7401. 5. Guzmn, J. A.; Mendoza, V.; Garca, E.; Garibay, C. F.; Olivares, L. Z.; Maldonado,

    L. A. Synth. Commun. 1995, 25, 2121. 6. Jung, M. E.; Lazarova, T. I. J. Org. Chem. 1997, 62, 1553. 7. Varma, R. S.; Naicker, K. P. Org. Lett. 1999, 1, 189. 8. Roy, A.; Reddy, K. R.; Mohanta, P. K.; Ila, H.; Junjappa, H. Synth. Commun. 1999,

    29, 3781. 9. Lawrence, N. J.; Rennison, D.; Woo, M.; McGown, A. T.; Hadfield, J. A. Bioorg.

    Med. Chem. Lett. 2001, 11, 51.