Ethyl (2R*,3S*)-3-hydroxy<2-(2)H>butanoate | 142612-32-6

• 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: Ethyl (2R*,3S*)-3-hydroxy<2-(2)H>butanoate
• 英文别名: rel-(2R,3S)-ethyl 2-deuterio-3-hydroxybutanoate；ethyl (2R,3S)-2-deuterio-3-hydroxybutanoate
• CAS: 142612-32-6；142612-36-0
• 化学式: C₆H₁₂O₃
• 分子量: 133.152
• InChiKey: OMSUIQOIVADKIM-CGEDHUKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  ethyl 3-hydroxybutyrate 在 偶氮二异丁腈 、 triphenylstannane-d₁ 、 lithium diisopropyl amide 作用下， 以 甲苯 为溶剂， 生成 Ethyl (2R*,3S*)-3-hydroxy<2-(2)H>butanoate
  参考文献：
  名称：

  Investigation of a model for 1,2-asymmetric induction in reactions of .alpha.-carbalkoxy radicals: a stereochemical comparison of reactions of .alpha.-carbalkoxy radicals and ester enolates

  摘要：

  The stereochemical course of reductions and allylations of alpha-carbalkoxy radicals with chiral centers at the beta-position are reported. Radicals without polar substituents, with alkoxyl or acetoxyl groups, and with hydroxyl groups at the beta-position were examined. Reactions showed selectivities ranging from low (50:50) to high (99:1). The results are discussed in terms of transition-state models that emphasize the importance of (1) allylic conformational analysis (minimization of A1,3 and A1,2 strain), (2) torisonal strain (minimization of eclipsed interactions), and (3) stereoelectronic effects.

  DOI：

  10.1021/jo00042a029

文献信息

• Diastereoselectivity in the Protonation of Ester Enolates. The Importance of Aggregation with LDA
  作者：Jerry R. Mohrig、Peter K. Lee、Karin A. Stein、Mark J. Mitton、Robert E. Rosenberg

  DOI：10.1021/jo00116a046

  日期：1995.6

  The effect of aggregation on the stereochemistry of electrophilic attack on ester enolate anions has been studied by comparing the diastereoselectivity of protonation of the LDA-generated dianion bf I 1 in THF/DMPU with the H/D exchange of 3 under non-ion-pairing conditions. The LDA results are consistent with proton transfer to the:enolate occurring preferentially from the tightly complexed secondary amine. Proton sources of varying steric requirements produced the same diastereomeric ratio, 63:37 2R*,3R*/2R*,3S* of 2. Added BuLi and the omission of DMPU gave the same diastereomeric mixture. In contrast to the LDA results, ethyl beta-hydroxy- and beta-alkoxybutyrates undergo base-catalyzed H/D exchange largely through antiperiplanar transition states, with diastereoselectivity opposite of that found in-the LDA-enolate protonation. Thus, the geometry of the LDA-enolate aggregate, rather than steric and electronic factors in the monomer, is responsible for the stereochemistry of enolate anion protonation. The lower diastereoselectivity in the H/D exchange of 6 in THF is accounted forby ion-pairing effects, as the use of Me(4)NOD produced 92% of the 2R*,3R* diastereomer; Use of polar solvents in the H/D exchange also raised the diastereoselectivity to a 10:1 ratio or higher.
• Investigation of a model for 1,2-asymmetric induction in reactions of .alpha.-carbalkoxy radicals: a stereochemical comparison of reactions of .alpha.-carbalkoxy radicals and ester enolates
  作者：David J. Hart、Ramanarayanan Krishnamurthy

  DOI：10.1021/jo00042a029

  日期：1992.7

  The stereochemical course of reductions and allylations of alpha-carbalkoxy radicals with chiral centers at the beta-position are reported. Radicals without polar substituents, with alkoxyl or acetoxyl groups, and with hydroxyl groups at the beta-position were examined. Reactions showed selectivities ranging from low (50:50) to high (99:1). The results are discussed in terms of transition-state models that emphasize the importance of (1) allylic conformational analysis (minimization of A1,3 and A1,2 strain), (2) torisonal strain (minimization of eclipsed interactions), and (3) stereoelectronic effects.