P-22 酵素機能を利用する高立体選択的キラルシントンの合成とその天然物合成への応用(ポスター発表の部)

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概要

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• One of the most efficient method to synthesize optically pure natural products is to start off with chiral synthon. We synthesized three new chiral synthons (2R,3R)-4, (4R,5S)-27, and (S)-(-)-34 on the basis of the following two concepts; (1) to utilize the highly stereoselective chemical method to establish the relative configuration, (2) to carry out the kinetic resolution of racemates by ester-cleaving enzymes (lipase) at the next step. The Zn(BH_4)_2 reduction of β-keto ester (±)-3 afforded the alcohol (±)-syn-1 in high diastereoselectivity. The saponification of the corresponding acetate (±)-4 using the lipase "Amano A" proceeded enantioselectively to give acetate (2R,3R)-4 (48% yield, >99%ee) and alcohol (2S,3S)-1 (51% yield, 94%ee). The epoxidation of methyl sorbate followed by addition of thiophenol provided (±)-22 stereospecifically. The enantioselective esterification of (±)-22 using the lipase "PL266" in the presence of isopropenyl acetate gave alcohol (4R,5S)-22 (49.7%, >99%ee) and acetate (4S,5R)-23 (50.2%, 98%ee). The successful conversion of C-S into C-O bond at C_4 chiral center in stereo retentive manner was carried out to give (4S,5S)-21 which was converted into ketal (4R,5S)-27 via three steps. The coupling reaction of methyl 4,5-epoxy-(2E)-pentenoate 33 and m-methoxy toluene in the presence of lewis acid provided two alcohols 34 (23%) and 35 (49%). The enantioselective hydrolysis of acetate (±)-36 derived from 34 using the lipase "MY-30" gave alcohol (S)-(-)-34 (85%ee). The enzymatic esterification of this chiral compound using same lipase achieved the enrichment of optical purity. In result, we obtained (S)-(-)-36 (94%ee). These chiral compound were applicable to the syntheses of (-)-Oudemansins A, B and X, L-Acosamine, and (S)-(+)-Curcudiol.

• 天然有機化合物討論会の論文
• 1994-09-20

著者

• 尾能 満智子

  東邦大薬

• 秋田 弘幸

  東邦大薬

• 尾能 満智子

  School Of Pharmaceutical Sciences Toho University

• 陳 政宇

  東邦大薬

• 南雲 紳史

  東邦大薬

• 梅澤 勲

  東邦大薬

• 南雲 紳史

  School Of Pharmaceutical Science Toho University

• Nagumo S

  School Of Pharmaceutical Science Toho University

• Akita H

  Toho Univ. Chiba Jpn

• Akita Hiroyuki

  School Of Pharmaceutical Science Toho University

• Nagumo S

  Hokkaido Coll. Pharmacy Otaru Jpn

• Umezawa I

  Riken Institute (the Institute Of Physical And Chemical Research):(present Address)fuji Yakuhin Co.

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