(S)-methyl 3-acetoxybutanoate | 53562-87-1

• 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: (S)-methyl 3-acetoxybutanoate
• 英文别名: (S)-methyl 3-hydroxybutanoate；(S)-3-acetoxy-butyric acid methyl ester；(S)-3-Acetoxy-buttersaeure-methylester；(+/-)-3-Acetoxy-buttersaeure-methylester；methyl (3S)-3-acetyloxybutanoate
• CAS: 53562-87-1
• 化学式: C₇H₁₂O₄
• 分子量: 160.17
• InChiKey: GSQSJDKJUCRGGT-YFKPBYRVSA-N

物化性质

• 沸点：
  131.5±13.0 °C(Predicted)
• 密度：
  1.057±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (S)-(+)-3-acetoxybutyric acid 生成 (S)-methyl 3-acetoxybutanoate
  参考文献：
  名称：

  FERRABOSCHI, PATRIZIA;GRISENTI, PARIDE;MANZOCCHI, ADA;SANTANIELLO, ENZO, J. CHEM. SOC. PERKIN TRANS. PT 1,(1990) N, C. 2469-2474

  摘要：

  DOI：

文献信息

• Over 98% Optical Yield Achieved by a Heterogeneous Catalysis. Substrate Design and Analysis of Enantio-Differentiating Factors of Tartaric Acid-Modified Raney Nickel Hydrogenation
  作者：Takashi Sugimura、Satoshi Nakagawa、Akira Tai

  DOI：10.1246/bcsj.75.355

  日期：2002.2

  Tartaric acid-modified Raney nickel (TA-MRNi) is a chiral heterogeneous catalyst for the hydrogenation of prochiral ketones. An optical yield (OY) of 86% with methyl acetoacetate (1) as a substrate was improved to 94–96% by employing β-keto esters having a proper bulkiness at the γ -position. The γ -bulkiness effect contributes to a high intrinsic enantio-differentiating ability (factor-i) of the TA-MRNi catalysis. Through the study, we found the best substrate, γ -cyclopropyl-β-keto ester, the hydrogenation of which resulted in 98.6% OY. This further improvement in the OY was ascribed to a smaller contribution of non-enantio-differentiating hydrogenation (N-site catalysis) due to the substrate-specific activation of the enantio-differentiating hydrogenation by the chiral modifier. The OY of the hydrogenation of 1 was analyzed by comparing with well-behaved β-keto esters, and the contribution of the factor-i and the N-site to the OY value was evaluated to deduce the origin of the enantiodifferentiation.

  酒石酸改性的Raney镍(TA-MRNi)是一种手性非均相催化剂，用于前手性酮的氢化反应。以乙酰乙酸甲酯(1)为底物，光学收率(OY)为86%，当采用在γ位置具有适当体积的β-酮酯时，OY提高至94-96%。γ体积效应有助于TA-MRNi催化剂具有高固有的手性区分能力(因子-i)。通过研究，我们发现最佳底物，即γ-环丙基-β-酮酯，其氢化反应的光学收率达到了98.6%。这一光学收率的进一步提升归因于底物特定的手性修饰剂激活手性区分氢化反应，从而减少了非手性区分氢化(N-位点催化)的贡献。通过与表现良好的β-酮酯进行比较，分析了1氢化反应的OY，并评估了因子-i和N-位点对OY值的贡献，从而推导出手性区分的起源。
• Axially chiral P-N ligands for the copper catalyzed β-borylation of α,β-unsaturated esters
  作者：William J. Fleming、Helge Müller-Bunz、Vanesa Lillo、Elena Fernández、Patrick J. Guiry

  DOI：10.1039/b900741e

  日期：——

  The synthesis and resolution of a new axially chiral Quinazolinap ligand are reported. The application of this and other related P-N ligands to the copper catalyzed β-borylation of α,β-unsaturated esters resulted in conversions of up to 100% and ee values of up to 79%. A diastereomerically pure palladacycle of the new ligand was characterised by X-ray crystallography.

  报道了一种新型轴手性喹唑啉啶配体的合成与解析。将该配体及其他相关P-N配体应用于铜催化的α,β-不饱和酯的β-硼化反应中，获得了高达100%的转化率和高达79%的ee值。通过X射线晶体学方法对新配体的一种纯对映异构钯环进行了表征。
• Synthesis of Novel Diastereomeric Diphosphine Ligands and Their Applications in Asymmetric Hydrogenation Reactions
  作者：Liqin Qiu、Jianying Qi、Cheng-Chao Pai、Shusun Chan、Zhongyuan Zhou、Michael C. K. Choi、Albert S. C. Chan

  DOI：10.1021/ol026817+

  日期：2002.12.1

  Diastereomeric biaryl diphosphine ligands 10 and 11 with added chiral centers on the backbone were synthesized. Substrate-directed asymmetric synthesis occurred in the coupling step of the preparation of the diastereomeric diphosphine oxides. The diastereomeric diphosphine oxides were easily separated by column chromatography with silica gel. Ruthenium catalysts containing these ligands were highly effective

  ［结构：见正文］合成了在主链上增加了手性中心的非对映体联芳基二膦配体10和11。在非对映体二膦氧化物的制备的偶联步骤中发生了底物定向的不对称合成。通过使用硅胶的柱色谱法容易地分离非对映体二膦氧化物。含有这些配体的钌催化剂在2-（6'-甲氧基-2'-萘基）丙酸和β-酮酸酯的氢化中非常有效。额外的手性中心对催化剂的对映选择性和活性有重大影响。
• Simplified preparation of chirally modified nickel catalyst for enantioselective hydrogenation: A step forward to industrial use
  作者：Tsutomu Osawa、I-Yin Sandy Lee、Shinji Ikeda、Takayuki Kitamura、Yoshihisa Inoue、Victor Borovkov

  DOI：10.1016/j.apcata.2012.08.035

  日期：2012.11

  photoelectron spectral examinations of chirally modified nickel catalysts obtained under the different modification conditions revealed that the chiral modification process itself plays a major role in activating the nickel surface whilst the pre-activation procedure is a less important factor. The corresponding enantio-differentiating hydrogenations of methyl acetoacetate in the liquid phase using the prepared

  通常通过将预活化的金属镍浸入对映纯的酒石酸的水溶液中来制备用于β-酮酸酯的对映体-区别氢化的手性改性的镍催化剂（所谓的“改性步骤”）。在预活化步骤中，镍前体通常在高达473 K的高温下用氢气处理。在不同改性条件下获得的手性改性镍催化剂的X射线光电子能谱检查表明，手性改性过程本身在活化镍表面上起主要作用，而预活化步骤则不太重要。
• Durability enhancement of chirally modified metallic nickel catalysts for enantioselective hydrogenation
  作者：Tsutomu Osawa、Tomoko Kizawa、I-Yin Sandy Lee、Shinji Ikeda、Takayuki Kitamura、Yoshihisa Inoue、Victor Borovkov

  DOI：10.1016/j.catcom.2011.08.006

  日期：2011.11

  Metallic Ni catalysts co-modified with (R,R)-tartaric acid and NaBr showed high enantioselectivity and durability upon hydrogenation of methyl acetoacetate to give methyl 3-hydroxybutyrate. The chirally modified catalyst prepared from 3-μm Ni powder was highly robust to maintain the hydrogenation activity and enantiodifferentiating ability for ca. 3 months under dry condition, which enables long-term

  用（R，R）-酒石酸和NaBr共改性的金属Ni催化剂在乙酰乙酸甲酯加氢生成3-羟基丁酸甲酯时显示出高的对映选择性和耐久性。由3-μm镍粉制备的手性改性催化剂具有很高的鲁棒性，可以保持氢化活性和对映体的对映体扩散能力。干燥条件下可存放3个月，可长期保存，因此有利于商业销售和工业应用。