ethyl (2R*,3R*)-2-benzyl-3-hydroxybutanoate

• 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*,3R*)-2-benzyl-3-hydroxybutanoate
• 英文别名: ethyl (2R,3R)-2-benzyl-3-hydroxybutanoate
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: NKARQSGHMCQMJP-ZYHUDNBSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.46
• 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 (2R*,3R*)-2-benzyl-3-hydroxybutanoate 在 咪唑 、 异丙基氯化镁 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 19.0h， 生成
  参考文献：
  名称：

  β-羟基酮的化学酶动态动力学不对称转化

  摘要：

  将钌和酶催化结合在一锅法中，实现 α-取代 β-羟基酮的高效 DYKAT。这种新开发的方案通过采用钌基外消旋催化剂，通过形成非手性 1,3-二酮中间体，实现底物的高效外消旋差向异构化，从而以高产率直接获得对映体纯和非对映体富集的 β-氧代乙酸酯。

  DOI：

  10.1002/chem.202102683
• 作为产物：
  描述：

  (2R,5R,6R)-5-Benzyl-2-(tert-butyl)-6-methyl-1,3-dioxan-4-on 在 硫酸 Dowex 50 W 作用下， 以 乙醇 为溶剂， 反应 16.0h， 生成 ethyl (2R*,3R*)-2-benzyl-3-hydroxybutanoate
  参考文献：
  名称：

  ?-Alkylierung von ?-Hydroxycarbons�uren �ber 1,3-Dioxan-4-on-Enolate

  摘要：

  Highly Diastereoselective α‐Alkylation of β‐Hydroxycarboxylic Acids Through Lithium Enolates of 1,3‐Dioxan‐4‐onesFrom serine, β‐hydroxyisobutyric acid (‘Roche’ acid) and β‐hydroxybutyric acid, the dioxanones 1–6 were prepared. The generation of the enolates of type I with LDA at −75° and alkylation gave products with trans‐configuration whereas protonation of the 5‐methyl‐substituted enolate allowed access to the cis‐configurated β‐hydroxybutyric‐acid derivative 12. Hydrolysis gave the free β‐hydroxy acids of ‘syn’‐and ‘anti’‐configuration. Alkylation of the 6‐unsubstituted dioxanones 1 and 3 yielded predominantly products resulting from attack in the cis‐position of the t‐Bu group. The ‘reactive’ conformation of the enolates involved is tentatively derived from the product configuration. The selectivity of the alkylation is also discussed in terms of the results of an ab‐initio calculation on the enolates M–P.

  DOI：

  10.1002/hlca.19880710527

文献信息

• Enantioselective and Diastereoselective Ir-Catalyzed Hydrogenation of α-Substituted β-Ketoesters via Dynamic Kinetic Resolution
  作者：Guoxian Gu、Jiaxiang Lu、Ouran Yu、Jialin Wen、Qin Yin、Xumu Zhang

  DOI：10.1021/acs.orglett.8b00433

  日期：2018.4.6

  An iridium/f-amphol catalytic system for the enantioselective hydrogenation of α-substituted β-ketoesters via dynamic kinetic resolution is reported. The desired anti products were obtained in high yields (up to 98%) with good diastereoselectivity (up to 96:4 diastereometic ratio (dr)) and excellent enantioselectivity (up to >99% enantiomeric excess (ee)). A catalytic model is proposed to explain the

  报道了用于通过动态动力学拆分对α-取代的β-酮酸酯进行对映选择性氢化的铱/ f-amphol催化体系。以高收率（高达98％），良好的非对映选择性（高达96：4的非对映比率（dr））和优异的对映选择性（高达> 99％的对映体过量（ee））获得所需的抗产物。提出了催化模型来解释立体选择性。
• Stereocontrol of palladium(ii)-catalysed aza-Claisen rearrangements using a combination of 1,3-allylic strain and a solvent mediated directing effect
  作者：Michael D. Swift、Andrew Sutherland

  DOI：10.1039/b613271e

  日期：——

  The use of a non-coordinating solvent for the aza-Claisen rearrangement of delta,epsilon-disubstituted acetimidates switches on a substrate directing effect that gives excellent stereoselectivity.

  使用非配位溶剂进行δ，ε-二取代的乙酰胺基的氮杂-克莱森重排会改变底物导向效果，从而产生出色的立体选择性。
• A recombinant ketoreductase tool-box. Assessing the substrate selectivity and stereoselectivity toward the reduction of β-ketoesters
  作者：Dunming Zhu、Chandrani Mukherjee、J. David Rozzell、Spiros Kambourakis、Ling Hua

  DOI：10.1016/j.tet.2005.10.044

  日期：2006.1

  The substrate selectivity and stereoselectivity of a series of ketoreductases were evaluated toward the reduction of two sets of beta-ketoesters. Both the structural variety at beta-position and the substituent at alpha-position greatly affected the activity and stereoselectivity of these ketoreductases. For the first set of beta-ketoesters, at least one ketoreductase was found that catalyzed the formation of either (D) or (L) enantiomer of beta-hydroxyesters from each substrate with high optical purity, with the only exception of ethyl (D)-3-hydroxy3-phenylpropionate. For the second set of beta-ketoesters with alpha-substituents, the situation is more complex. More commonly, a ketoreductase was found that formed one of the four diastereomers in optically pure form, with only a few cases in which enzymes could be found that formed two or more of the diastereomers in high optical purity. The continued development of new, more diverse ketoreductases will create the capability to produce a wider range of single diastereomers of 2-substituted-3-hydroxy acids and their derivatives. (c) 2005 Elsevier Ltd. All rights reserved.
• Reversed Stereochemical Control in the Presence of CeCl₃ and TiCl₄ in the Lewis Acid Mediated Reduction of α-Alkyl-β-keto Esters by Metal Hydrides. A General Methodology for the Diastereoselective Synthesis of <i>s</i><i>yn</i>- and <i>a</i><i>nti</i>-α-Alkyl-β-hydroxy Esters
  作者：Enrico Marcantoni、Sara Alessandrini、Marco Malavolta、Giuseppe Bartoli、Maria Cristina Bellucci、Letizia Sambri、Renato Dalpozzo

  DOI：10.1021/jo9821574

  日期：1999.3.1

  The Lewis acid-mediated reduction of alpha-alkyl-beta-keto esters has been shown to proceed by different stereochemical control depending on the nature of the metal atom. Strongly chelating TiCl4 led to the syn isomer in high diastereomeric excess in noncoordinating solvents (CH2Cl2) at -78 degrees C with BH3. py as reducing agent, while nonchelating CeCl3 gave a high excess of the anti isomer in coordinating solvents (THF) at the same temperature with lithium triethylborohydride (LiEt3BH) as reducing agent. The methodology has been successfully utilized for obtaining important syn- and anti-alpha-alkyl-beta-hydroxy esters with high diastereoselectivity.
• ZIMMERMANN, JURG;SEEBACH, DIETER;HA, TAE-KYU, HELV. CHIM. ACTA, 71,(1988) N 5, C. 1143-1155
  作者：ZIMMERMANN, JURG、SEEBACH, DIETER、HA, TAE-KYU

  DOI：——

  日期：——