Selenium Dioxide Oxidation of Steroidal 1,4-Dien-3-Ones. A Simple and Convenient Route to 6-Hydroxycorticosteroids

References

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• In relation to this, the 9α, 11α-oxide 22 was subjected to allylic oxidation (3.0 eq SeO2, dioxane, 100°C, 42 h), but no product was obtained
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• In 9β, 11β-oxides, however, the differences were small and irregular, presumably because of B-ring distortion and different degrees of long-range shielding by the oxide ring system, e.g. 1a: δ 4.71 (ddd, 1H, J=10, 5, and 1.5 Hz, 6β-H), 6.48 (t, 1H, J=1.5 Hz, 4-H); 1b: δ 4.50 (ddd, 1H, J=10, 5, and 1.5 Hz, 6α-H), 6.48 (t, 1-H, J=1.5 Hz, 4-H); 7a: δ 4.55 (ddd, 1H, J=10, 5, and 1.5 Hz, 6β-H), 6.50 (t, 1H, J=1.5 Hz, 4-H); 7b: δ 4.42 (t, 1H, J=2 Hz, 6α-H), 6.17 (t, 1H, J=2 Hz, 4-H)
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• Details of the X-ray analyses will be reported elsewhere
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• Similarly, the 1,2-dihydro derivatives of betamethasone 21-acetate, dexamethasone 17-propionate 21-acetate (3.3 eq SeO2, dioxane, 80°C, 2.5 h), and betamethasone 17,21-dipropionate (3 eq SeO2, dioxane, 110°C, 2.5 h) were converted to the corresponding 6β-alcohols in 22%, 23%, and 25% yields, respectively
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• Sharpless , K. B. and Lauer , R. F. 1972 . J. Am. Chem. Soc. , 94 : 7154 If the 6-hydroxylation reaction can be rationalized by assuming initial formation of an ene product, e.g. the 5-ene-4-seleninic acid, followed by its [2,3]-sigmatropic rearrangement, the stereochemistry may be determined by the orientation of the 4-seleninic group first introduced in the ene reaction. See also
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