rel-(2R,3S)-ethyl 2-deuterio-3-methoxybutanoate | 101226-81-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: rel-(2R,3S)-ethyl 2-deuterio-3-methoxybutanoate
• 英文别名: ethyl (2R,3S)-2-deuterio-3-methoxybutanoate
• CAS: 101226-81-7
• 化学式: C₇H₁₄O₃
• 分子量: 147.178
• InChiKey: OKVHMCVJTGMHIZ-WRJDEACLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  ethyl 3-hydroxy-2-(phenylselenyl)butanoate 在 偶氮二异丁腈 、 1,8-双二甲氨基萘 、 triphenylstannane-d₁ 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 rel-(2R,3S)-ethyl 2-deuterio-3-methoxybutanoate
  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 of Enolate Anion Protonation. H/D Exchange of β-Substituted Ethyl Butanoates in Ethanol-<i>d</i>
  作者：Jerry R. Mohrig、Robert E. Rosenberg、John W. Apostol、Mark Bastienaansen、Jordan W. Evans、Sonya J. Franklin、C. Daniel Frisbie、Sabrina S. Fu、Michelle L. Hamm、Christopher B. Hirose、David A. Hunstad、Thomas L. James、Randall W. King、Christopher J. Larson、Hallie A. Latham、David A. Owen、Karin A. Stein、Ronald Warnet

  DOI：10.1021/ja962631s

  日期：1997.1.1

  The stereochemistry of base-catalyzed H/D exchange on 13 β-substituted ethyl butanoates in ethanol-d has been studied in order to analyze the steric and electronic factors which control the diastereoselectivity of electrophilic attack on enolate anions. Electrophilic deuteration of the enolate anion also determines the stereoselectivity of 1,4-conjugate addition of ethanol-d to α,β-unsaturated esters

  研究了乙醇-d 中 13 β-取代丁酸乙酯的碱催化 H/D 交换的立体化学，以分析控制亲电攻击烯醇阴离子的非对映选择性的空间和电子因素。烯醇阴离子的亲电氘化也决定了 1,4-共轭加成乙醇-d 到 α,β-不饱和酯的立体选择性。选择严格排除离子配对和聚集影响的实验条件。研究表明，立体电子因素通常比立体效应产生更高的立体选择。C-3 处带负电的杂原子取代基产生 10:1 的 2R*,3R*/2R*,3S*2-氘代丁酸酯。在最稳定的亲电攻击过渡态中，这些带负电的取代基占据形成 C-D 键的反面位置。只有用 β-叔丁基取代基才能产生高立体选择性，并且它随着递减速度的降低而迅速下降。
• 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.