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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 19, 1989 - Issue 5-6
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Original Articles

Swern Oxidation of α-Ketols to α-Diketones1

, &
Pages 777-785 | Received 25 Jul 1988, Published online: 24 Oct 2006

References

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  • Rigby , W. 1951 . J. Chem. Soc. , : 793 For leading references to procedures for the oxidation of 1 to 2 using bismuth trioxide in acetic acid: (a);
  • Hoden , B. and Rigby , W. 1951 . ibid. , : 1924
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  • Corey , E. J. , Tius , M. A. and Das , J. 1980 . J. Am. Chem. Soc. , 102 : 1742 Using selenium dioxide: De Borger, L.; Anteunis, M.; Lammens, H.; Verzele, M. Bull. Soc. Chim. Belg. 1964, 73, 73. Using manganese dioxide: Papadopoulos, E. P.; Jarrar, A.; Issidorides, C. H. J. Org. Chem. 1966, 31, 615. Using cupric acetate: (a) Weiss, M.; Appel, M. J. Am. Chem. Soc. 1948, 70, 3666;
  • Weiss , M. and Appel , M. 1949 . ibid. , 71 : 2269 Using bromine/sodium hydroxide: Utaka, M.; Matsushita, S.; Takeda, A. Chem. Lett. 1980, 779.
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  • VanDyke , M. and Pritchard , N. D. 1967 . J. Org. Chem. , 32 : 3204 For a similar oxidation of benzoin and related systems using DMSO/acetic anhydride, see
  • Govindan , S. V. and Fuchs , P. L. 1988 . J. Org. Chem. , 53 : 2593
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  • Vedejs , E. , Engler , D. A. and Telshchow , J. E. 1978 . J. Org. Chem. , 43 : 188 The α-ketols used in this study were purchased or prepared using a standard MoOPH oxidation of the corresponding ketone:
  • Rao , D. V. , Stuber , F. A. and Ulrich , H. 1979 . J. Org. Chem. , 44 : 456
  • 3α,16α-Dihydroxy-5α-androstan-17-one: IR (KBr) 3520, 3350, 1735 cm−1; 1H NMR (CDCl3) δ 0.79 (s, 3, CH3), 0.94 (s, 3, CH3), 4.02–4.07 (m, 1, OH), 4.30–4.38 (m, 1, CHOH); exact mass spectrum calcd for C19H30O3 306.2196, found 306.2194. 16α-Hydroxy-5α-androstane-3,17-dione: IR (CCl4) 3400, 1750, 1718 cm−1; 1H NMR (CDCl3) δ 0.97 (s, 3, CH3), 1.03 (s, 3, CH3), 4.32–4.42 (m, 1, CHOH); exact mass spectrum calcd for C19H28O3 304.2039, found 304.2037.
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  • Okino , H. , Uchida , S. and Matsushita , K. 1984 . Jpn. Kokai Tokkyo Koho JP61 56,146[86 56,146]((Chem. Abstr. 1986, 105, 171912q).
  • Diketone 1m was prepared from i (see reference 1) using: (1) K2CO3, THF, MeOH (86%); (2) PhOC(S)Cl, Py, 0 [ddot]C (93%); (3) nBu3SnH, AIBN, benzene (83%); (4) nBu4NF, THF (56%); and (5) PCC, NaOAc, CH2Cl2 (76%).
  • Wagner , P. J. , Zepp , R. G. , Liu , K.-C. , Thomas , M. , Lee , T.-J. and Turro , N. J. 1976 . J. Am. Chem. Soc. , 98 : 8125
  • Snell , J. M. and McElvain , S. M. 1931 . J. Am. Chem. Soc. , 53 : 750
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  • Mori , H. , Gandi , V. S. and Schwank , E. 1962 . Chem. Pharm. Bull. , 10 : 842

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