dimethyl (2S,3S)-2-allyl-3-hydroxyglutarate | 147528-53-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: dimethyl (2S,3S)-2-allyl-3-hydroxyglutarate
• 英文别名: (2S,3S)-2-allyl-3-hydroxyglutarate；dimethyl (2S,3S)-3-hydroxy-2-prop-2-enylpentanedioate
• CAS: 147528-53-8
• 化学式: C₁₀H₁₆O₅
• 分子量: 216.234
• InChiKey: GQULIZOFIQJCMQ-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  dimethyl (2S,3S)-2-allyl-3-hydroxyglutarate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 以85%的产率得到(2R,3S)-2-allyl-1,3,5-trihydroxypentanol
  参考文献：
  名称：

  Reduction of 2-substituted 3-oxoglutarates mediated by baker's yeast. Variation in enantioselectivity without corresponding variation in diastereoselectivity

  摘要：

  The reduction of 2-substituted 3-oxoglutarates by yeast yields a new class of chiral building blocks, 2-allyl- and 2-propargyl-3-hydroxyglutarates. These are useful as starting points for the synthesis of, inter alia, branched chain analogs of sugars and nucleosides. When allyl is the side chain, the principal product has the absolute configuration (2S,3S), proven by correlation with a compound whose absolute configuration was established by crystallography. Several features of this yeast-mediated reduction are noteworthy. First, its diastereoselectivity is higher than its enantioselectivity, especially with the propargyl side chain. Further, with all substrates, variation in enantioselectivity is not manifested by a variation in diastereoselectivity. This example therefore serves as a warning for those using yeast-mediated reactions that diastereoselectivity cannot be accepted as a substitute for direct measurements of enantioselectivity, even with analogous substrates and similar reaction conditions. Finally, an unexpected metabolism of impurities in the starting material by the yeast made the overall transformation preparatively useful.

  DOI：

  10.1021/jo00060a048
• 作为产物：
  描述：

  1,3-丙酮二羧酸二甲酯 、 3-溴丙烯 在 sodium methylate 作用下， 生成 3-羟基戊二酸二甲酯 、 2-allyl-3-oxohept-6-enoic acid methyl ester 、 dimethyl (2S,3S)-2-allyl-3-hydroxyglutarate 、 dimethyl (2R,3R)-2-allyl-3-hydroxyglutarate
  参考文献：
  名称：

  Reduction of 2-substituted 3-oxoglutarates mediated by baker's yeast. Variation in enantioselectivity without corresponding variation in diastereoselectivity

  摘要：

  The reduction of 2-substituted 3-oxoglutarates by yeast yields a new class of chiral building blocks, 2-allyl- and 2-propargyl-3-hydroxyglutarates. These are useful as starting points for the synthesis of, inter alia, branched chain analogs of sugars and nucleosides. When allyl is the side chain, the principal product has the absolute configuration (2S,3S), proven by correlation with a compound whose absolute configuration was established by crystallography. Several features of this yeast-mediated reduction are noteworthy. First, its diastereoselectivity is higher than its enantioselectivity, especially with the propargyl side chain. Further, with all substrates, variation in enantioselectivity is not manifested by a variation in diastereoselectivity. This example therefore serves as a warning for those using yeast-mediated reactions that diastereoselectivity cannot be accepted as a substitute for direct measurements of enantioselectivity, even with analogous substrates and similar reaction conditions. Finally, an unexpected metabolism of impurities in the starting material by the yeast made the overall transformation preparatively useful.

  DOI：

  10.1021/jo00060a048

文献信息

• Determination of the Absolute Configuration of Dimethyl (2S,3S)-2-Allyl-3-hydroxyglutarate: A Chiral Building Block for Preparing Branched-Chain Nucleoside Analogues
  作者：Tuncer Arslan、Bernardo Herradon、Bernd W. Schweizer、Steven A. Benner

  DOI：10.1002/hlca.19930760821

  日期：1993.12.15

  A yeast-catalyzed reduction of dimethyl (2S,3S)-2-allyl-3-hydroxyglutarate is the key step in the preparation of bis-homo, branched-chain nucleoside analogues. To establish unambiguously the stereochemical course of the microbial reaction, the product has been converted to a derivative esterified with camphanoyl chloride, and a crystal structure of the derivative solved.

  酵母催化还原（2 S，3 S）-2-烯丙基-3-羟基戊二酸二甲酯是制备双均质支链核苷类似物的关键步骤。为了明确地确定微生物反应的立体化学过程，已将产物转化为用樟脑酰氯酯化的衍生物，并解析了该衍生物的晶体结构。
• Reduction of 2-substituted 3-oxoglutarates mediated by baker's yeast. Variation in enantioselectivity without corresponding variation in diastereoselectivity
  作者：Tuncer Arslan、Steven A. Benner

  DOI：10.1021/jo00060a048

  日期：1993.4

  The reduction of 2-substituted 3-oxoglutarates by yeast yields a new class of chiral building blocks, 2-allyl- and 2-propargyl-3-hydroxyglutarates. These are useful as starting points for the synthesis of, inter alia, branched chain analogs of sugars and nucleosides. When allyl is the side chain, the principal product has the absolute configuration (2S,3S), proven by correlation with a compound whose absolute configuration was established by crystallography. Several features of this yeast-mediated reduction are noteworthy. First, its diastereoselectivity is higher than its enantioselectivity, especially with the propargyl side chain. Further, with all substrates, variation in enantioselectivity is not manifested by a variation in diastereoselectivity. This example therefore serves as a warning for those using yeast-mediated reactions that diastereoselectivity cannot be accepted as a substitute for direct measurements of enantioselectivity, even with analogous substrates and similar reaction conditions. Finally, an unexpected metabolism of impurities in the starting material by the yeast made the overall transformation preparatively useful.