76 キラルな多官能性シクロペンタンの合成と天然物合成への応用(口頭発表の部)
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概要
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Chiral, highly functionalized cyclopentanes seem to be attractive synthons for the syntheses of natural products containing a five-membered ring. During a detailed examination on the cyclization of 1,4-diketones 1 to cyclopentenones 2, we have found that two oxygenated products (4,5) are formed when the purification by column chromatography on silica gel takes a long time. To prepare chiral 4a, microbial reduction was examined. On screening of microbial reduction of (±)-4a using 40 species of yeasts, Rodotorula rubra.was found to be effective for the kinetic resolution, and highly opticaly pure products (>99% ee) were obtained. The absolute stereochemistry was determined by using the exciton chirality method. As the application of the easily prepared chiral synthon (+)-4a, we have achieved the formal syntheses of (-)-α- and (+)- β-cuparenone (16,17). One of the structural features in cuparene family is vicinal quaternary carbons on five-membered ring. The quaternary carbon with p-tolyl function could be nicely constructed by stereoselective 1,4-addition of (p-Tol)_2Zn to (+)-4a. The key intermediate β-ketol 21 obtained from (+)-4a was successfully converted to the Meyers' intermediate (+)-25 and to the Greene's intermediate (+)-28, respectively. In a similar manner, PGE_1 methyl ester was prepared. The oxygenated product 7 as a starting material was reduced stereoselectively to 29. LiBH_4 reduction of 29 gave a desired tetraol 30, which was converted to the enone 31 via protection of 1,2-diol, chemoselective oxidation with RuCl_2(PPh_3)_3 and introduction of ω-chain. The major product, 32, in the reduction of 31 with TLBH was converted to PGE_1 methyl ester 34 by usual manners.
- 天然有機化合物討論会の論文
- 1988-09-26
著者
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酒井 浄
Faculty of Pharmaceutical Sciences, Kyushu University
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酒井 浄
Faculty Of Pharmaceutical Sciences Kyushu University
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末宗 洋
九大・薬
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酒井 浄
九大・薬
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岡野 耕二
九大・薬
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末宗 洋
九州大学薬学部
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岡野 耕二
Life Science Research Laboratory Japan Tobacco Inc.
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末宗 洋
九州大学大学院薬学府
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末宗 洋
九州大学大学院薬学研究院
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