Ethyl <2,2-²H₂>-3-hydroxybutanoate | 128484-54-8

• 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: Ethyl <2,2-²H₂>-3-hydroxybutanoate
• 英文别名: Ethyl 3-hydroxy<2,2-(2)H2>butanoate；Ethyl [2,2-²H₂]-3-hydroxybutanoate；Ethyl 2,2-dideuterio-3-hydroxybutanoate
• CAS: 128484-54-8
• 化学式: C₆H₁₂O₃
• 分子量: 134.144
• InChiKey: OMSUIQOIVADKIM-APZFVMQVSA-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

• 作为反应物：
  描述：

  Ethyl <2,2-²H₂>-3-hydroxybutanoate 在 N,N-二甲基丙烯基脲 、 乙醇 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.75h， 生成 Ethyl (2R*,3S*)-3-hydroxy<2-(2)H>butanoate 、 Ethyl (2R*,3R*)-3-hydroxy<2-(2)H>butanoate
  参考文献：
  名称：

  Diastereoselectivity in the Protonation of Ester Enolates. The Importance of Aggregation with LDA

  摘要：

  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.

  DOI：

  10.1021/jo00116a046
• 作为产物：
  描述：

  乙酰乙酸乙酯 在 sodium tetrahydroborate 作用下， 生成 Ethyl <2,2-²H₂>-3-hydroxybutanoate
  参考文献：
  名称：

  Diastereoselectivity in the Protonation of Ester Enolates. The Importance of Aggregation with LDA

  摘要：

  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.

  DOI：

  10.1021/jo00116a046

文献信息

• Castle, Lyle W.; Hayes, Roger N.; Gross, Michael L., Journal of the Chemical Society. Perkin transactions II, 1990, # 2, p. 267 - 271
  作者：Castle, Lyle W.、Hayes, Roger N.、Gross, Michael L.

  DOI：——

  日期：——
• 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.