Studies on Steroids. XLV. Synthesis of the Four Stereoisomers of 20,22-Dihydroxycholesterol
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概要
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The four stereoisomers of 20,22-dihydroxycholesterol 9,10,17 and 19 were synthesized from pregnenolone. Vinylation of the 3,5-cyclo derivative 1 of pregnenolone gave the [20S]-carbinol 2,which was then oxidized with m-chloroperbenzoic acid to afford the [22S]-22,23-epoxide 3 and its [22R]-isomer 4 (7 : 2). Reaction of 3 and 4 with i-Bu_2CuLi followed by acid treatment yielded 20R, 22S-dihydroxycholesterol 9 and its 20R, 22R-isomer 10,respectively. The latter triol 10 was more effectively prepared by a Grignard reaction on the [20S]-20-formyl-carbinol 14,which was derived from pregnenolone THP ether 12,through the 1,3-dithiane derivative 13. Oxidation of 20-dehydrocholesterol acetate 16 with OsO_4 gave stereoselectively the 20S, 22S-glycol 17 (R=Ac). Treatment 17 (R=Ac) with N-chlorosuccinimide-dimethylsulfide followed by reduction with LiAlH_4 afforded 20S, 22R-dihydroxycholesterol 19 together with the 20S, 22S-isomer 17 (R=H) (3 : 2). Acid-catalyzed epoxide opening reactions of 20,22-epoxycholesterols were also discussed.
- 公益社団法人日本薬学会の論文
- 1977-10-25
著者
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佐藤 晋
Laboratory Of Chemistry For Natural Products Tokyo Institute Of Technology
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池川 信夫
Department Of Chemistry Tokyo Institute Of Technology
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池川 信夫
Laboratory Of Chemistry For Natural Products Tokyo Institute Of Technology
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森崎 益雄
Laboratory of Chemistry for Natural Products, Tokyo Institute of Technology
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