Chiral building-blocks by chemoenzymatic desymmetrization of 2-ethyl-1,3-propanediol for the preparation of biologically active natural products |
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| Institution: | 1. Industrial Research Institute of Nonwovens & Technical Textiles, College of Textiles & Clothing, Qingdao University, Qingdao 266071, China;2. Collaborative Innovation Center for Nanomaterials & Devices, College of Physics, Qingdao University, Qingdao 266071, China;1. Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810, Japan;2. Watarase Research Center, Kyorin Pharmaceutical Co., Ltd., Nogi 2399-1, Nogi-machi, Shimotsuga-gun, Tochigi 329-0114, Japan;3. Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan;1. State Key Laboratory of Phytochemistry and Plant Resources in West China, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming 650204, People''s Republic of China;2. College of Pharmacy, Chengdu University of Traditional Chinese Medicine, Chengdu 610075, People''s Republic of China;3. Institute of Materia Medica, Chinese Academy of Medical Sciences, Beijing 100050, People''s Republic of China;4. Key Laboratory of Regenerative Biology and Institute of Chemical Biology, Guangzhou Institutes of Biomedicine and Health, Chinese Academy of Sciences, Guangzhou 510530, People''s Republic of China;5. Key Laboratory of Animal Models and Human Disease Mechanisms of the Chinese Academy of Sciences & Yunnan Province, Kunming Institute of Zoology, Kunming 650223, People''s Republic of China;6. Kunming College of Life Science, University of Chinese Academy of Sciences, Beijing 100039, People''s Republic of China |
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| Abstract: | 2-Ethyl-1,3-propanediol 1 and its related di-O-acetate 2 were desymmetrized by partial chemoenzymatic acetylation and deacetylation, by Pseudomonas fluorescens lipase (Amano P.; PFL), to (R)-1-O-acetyl-2-ethyl-1,3-propanediol 3. On treatment of 3 with I2/Ph3P/imidazole the related (S)-1-O-acetyl-2-ethyl-3-iodopropanol 4 was obtained and transformed into the corresponding triphenylphosphonium salt 5. Reaction of (S)-3-acetoxy-2-ethylpropylidene]triphenylphosphorane 6, prepared from 5, with 2,3:4,5-di-O-isopropylidene-β-d-arabino-hexos-2-ulopyranose 7 gave (Z)-3-C-acetoxymethyl-1,2,3,4,5-pentadeoxy-6,7:8,9-di-O-isopropylidene-β-d-manno-dec-4-ene-6-ulo-6,10-pyranose 8 which was hydrogenated to 9 and subsequently deacylated to 10. Treatment of 10 with Me2CO/H+ caused a rearrangement to (3R,4R,5S,6R,9R)-9-ethyl-5-hydroxy-3,4-isopropylidenedioxy-1,7-dioxaspiro5.5]undecane 11, which closely matched the skeleton of the talaromycins. |
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