Stereospecific 1,2-Hydride Shift in the Rearrangement of 16β-Hydroxy-17-oxo Steroids to 17β-Hydroxy-16-ones with Acid and Base(Organic,Chemical)
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概要
- 論文の詳細を見る
When 16β-hydroxy-5α-androstan-17-one (2a) and its 16α-deuterio derivative (2a-16-d) were separately treated with H_2SO_4 or NaOH, compound 2a was rearranged to the 17β-hydroxy-16-oxo isomer (3a) with a marked kinetic deuterium isotope effect at the 16-position (k_H/k_D=4.5 or 3.0). The product 3a obtained from compound 2a-16-d retained deuterium at C-17 to the extent of 16-65% while no significant loss of the isotope from the substrate was observed during the reaction. Isotope-labeling experiments showed that the intramolecular 1,2-hydride shift is principally involved in the ketol rearrangement, and that the 16-oxo function of compound 3a enolizes preferentially, toward the C-17 position rather than the C-15 position under the above conditions.
- 公益社団法人日本薬学会の論文
- 1987-12-25
著者
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沼沢 光輝
Tohoku Pharmaceutical University
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沼沢 光輝
Tohoku College Of Pharmacy
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Nagaoka M
Tohoku Pharmaceutical Univ. Sendai Jpn
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Nagaoka Masao
Tohoku College Of Pharmacy:sankyo Co. Ltd.
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睦見 綾子
Tohoku College of Pharmacy
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長岡 正男
Tohoku College of Pharmacy
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