The transformation of jervine into 18-functional D-homo-C-norsteroids. IV. The transformation of jervine into (20R)-18,20.BETA.-epoxy-3.BETA.-hydroxy-17.BETA.-ethyletiojervan-18-one 3-acetate via (20R)-18,20.BETA.-epoxy-3.BETA.-hydroxy-12.ALPHA.,17.BETA.-

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概要

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• Catalytic hydrogenation of (22<I>S</I>,25<I>S</I>)-<I>N</I>-acetyl-3β,23β-dihydroxyveratra-5,13(17)-dien-11-one 3-acetate over rhodium-platinum catalyst in acetic acid gave (22<I>S</I>,25<I>S</I>)-N-acetyl-3β,23β-dihydroxyveratranin-11 -one 3-acetate (<B>2</B>) in <I>ca</I> 70% yield, together with two minor products. Irradiation of <B>2</B> in benzene containing mercury(II) oxide and iodine gave 20-formyl-3β-hydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (<B>5</B>) in 43% yield, accompanied by the 17-epimer of (22<I>S</I>,23<I>R</I>,25<I>S</I>)-<I>N</I>-acetyl-3β-hydroxy-5α-jervanin-11-one 3-acetate (4%). Aldehyde <B>5</B> was transformed into 3β-hydroxy-12α,17β-ethyletiojervane-11,20-dione 3-acetate (<B>15</B>) (79% yield) by photo- or coppercatalysed oxygenation of the corresponding enamine. Reduction of <B>15</B> with sodium borohydride gave 3β,20β-dihydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (<B>17</B>) as a major product (69%), together with the 20-epimer. The hypoiodite reaction of <B>17</B> gave 18,20β-epoxy-3β-hydroxy-17β-ethyl-12α-etiojervan-11-one 3-acetate (<B>19</B>) in 92% yield. Hydrolysis of <B>19</B> resulted in the isomerization of the C/D ring junction to give 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-11 -one (<B>20</B>), the first 18-functional C/D <I>trans</I> <I>D</I>-homo-<I>C</I>-norsteroid ever prepared. Wolff-Kishner reduction of <B>20</B> gave the corresponding 11-deoxo compound; its acetylation followed by oxidation yielded 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-18-one 3-acetate. The 11-oxo function of <B>19</B> can be reduced quite easily with lithium aluminum hydride to give the corresponding 11β-ol.

• 公益社団法人 日本化学会の論文

著者

• Ono Hitoshi

  Department Of Animal Reproduction School Of Veterinary Medicine Obihiro Zootechnical College

• Masamune Tadashi

  Department Of Chemistry Faculty Of Science Hokkaido University

• Suginome Hiroshi

  Department of Chemistry, Faculty of Science

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