12 微生物還元を利用する光学活性有用化合物の合成およびその天然物合成への応用
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概要
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In the field of synthesis of polyoxoantibiotics or the related polyfunctional natural products, the use of optically active compounds as a starting material is known to be quite advantageous. We now report the synthesis of optically active I, having the 2-methyl, 3-hydroxy moiety involved in I, based on the asymmetric reduction of the corresponding α-methyl β-keto ester II by microorganisms. 1. Microbiological asymmetric reduction of Dimethyl 2-methyl-3-oxo succinate 1 and Diethyl 2-methyl-3-oxo succinate 12 Asymmetric reduction of 1 by Saccharomyces cerevisiae gave the syn-2(2R,3R; 65 %ee) and the anti-3(2S,3R; 20 %ee). The stereostructure and the optical purity of the products was determined by means of 400MHz NMR spectroscopy. 2. Microbiological asymmetric reduction of methyl 2-methyl-3-(2-furyl)-3-oxo propionate 15 In order to obtain four functionalized chiral synthons (16, 17, 18, 19), asymmetric reduction of 15 was carried out. Kloeckera saturnus was found to give (S)-alcohols (16 and 18), while Saccharomyces delbrueckii or Saccharomyces fermentati afforded the opposite (R)-alcohols (17 and 19). Mass production of each isomers was undertaken and both chemical yield and optical yield (16; 83 %ee, 18; 73 %ee, 17; >99 %ee, 19; 98 %ee) were improved. In these cases, syn(16, 17)-anti(18, 19)-isomers are separable by usual Silica gel chromatography. 3. Determination of absolute structure of Oudemansin 25 For the purpose of determining an absolute structure of Oudemansin 25, the synthesis of optically active intermediates 29 or 30 was undertaken. Treatment of Me ester 26 with Saccharomyces cerevisiae gave the syn-29(2S,3R), while reduction of Et ester 27 with Candida albicans afforded the antipode 35(2R,3S). Optical yields of 29 (>99%ee) and 35 (97%ee) were extremely high in both cases.
- 天然有機化合物討論会の論文
- 1982-09-10
著者
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秋田 弘幸
理研
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大石 武
理研
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掘越 弘毅
理研・微生物
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秋田 弘幸
School Of Pharmaceutical Science Toho University
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秋田 弘幸
理化学研究所
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越地 弘子
Synthetic Organic Chemistry Laboratory The Institute Of Physical And Chemical Research (riken Instit
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掘越 弘毅
理研:微生物生態学研究室
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古市 昭也
理研
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越地 弘子
理研
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掘越 弘毅
理研
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古市 昭也
Synthetic Organic Chemistry Laboratory The Institute Of Physical And Chemical Research (riken Instit
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