(S)-mandelic acid n-butyl ester | 74879-33-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-mandelic acid n-butyl ester
• 英文别名: (S)-(+)-butyl mandelate；S-(+)-n-butyl mandelate；(S)-(+)-mandelate de n-butyle；n-butyl mandelate；Butyl (s)-mandelate；butyl (2S)-2-hydroxy-2-phenylacetate
• CAS: 74879-33-7
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: QLVXFMSPNHAPMO-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  (S)-mandelic acid n-butyl ester 在 mercury(II) diacetate 、 Eu(fod)3 作用下， 以 正己烷 为溶剂， 反应 72.0h， 生成 (4R,6R)-6-((S)-Butoxycarbonyl-phenyl-methoxy)-4-phenyl-5,6-dihydro-4H-pyran-2-carboxylic acid (1R,2S,5R)-2-isopropyl-5-methyl-cyclohexyl ester
  参考文献：
  名称：

  Synthèse asymétrique et configuration absolue de dihydropyranes substitués, par hétérocycloaddition intermoléculaire d'éthers vinyliques chiraux

  摘要：

  The alkyl vinyl ethers 2b-8b (deriving from the alcohols 2a-8a) smoothly reacted with methyl E-benzylidenepyruvate 10 in the presence of catalytic amounts of Eu(fod)(3) or Yb(fod)(3) in refluxing hexane, thus leading to the dihydropyran endo adducts 13-19 in high yields (80-95%). The endo-cycloadducts 13-17 were obtained with diastereofacial selectivities (ds) ranging from 76/24 to 87.5/12.5. Asymmetric induction was found to culminate with the vinyl ether (-)-7b deriving from n-butyl (R)-(-)-mandelate : the best ds (92.5/7.5) was obtained for the corresponding adduct 18 after 6 days at room temperature. The absolute configurations of the major isomers of the dihydropyrans 16-18, 20 and 21 were established by oxydative degradation to optically active alpha-phenylsuccinic acid derivatives.

  DOI：

  10.1016/s0040-4020(01)85370-9
• 作为产物：
  描述：

  alpha-羟基-苯乙酸丁酯 在 yeast lipase 、 三乙胺 、 正丁醇 作用下， 以 异丙醚 为溶剂， 反应 31.0h， 生成 (S)-mandelic acid n-butyl ester
  参考文献：
  名称：

  Resolution of secondary alcohols using lipase in diisopropyl ether

  摘要：

  DOI：

  10.1021/jo00271a042

文献信息

• Efficient mercury-free preparation of vinyl and isopropenyl ethers of chiral secondary alcohols and α-hydroxyesters
  作者：Gilles Dujardin、Sandrine Rossignol、Eric Brown

  DOI：10.1016/0040-4039(95)00087-s

  日期：1995.3

  acetals 2a-h and 5a-d, readily deriving from the α-chiral alcohols 1a-h and ethyl vinyl ether or isopropenyl methyl ether, underwent selective elimination of primary alcohol upon treatment with triethylamine and trimethylsilyl trifluoromethanesulfonate, and thus afforded good to high yields of the chiral enol ethers 3a-h and 6a-d, respectively.

  易于从α-手性醇1a-h和乙基乙烯基醚或异丙烯基甲基醚衍生而来的混合缩醛2a-h和5a-d，在用三乙胺和三甲基甲硅烷基三氟甲磺酸酯处理后，选择性地除去了伯醇，因此得到了良好的高分别得到手性烯醇醚3a-h和6a-d的产率。
• Autoamplification-Enhanced Oxidative Kinetic Resolution of <i>sec</i> -Alcohols and Alkyl Mandelates, and its Kinetic Model
  作者：Evgenii P. Talsi、Konstantin P. Bryliakov

  DOI：10.1002/cctc.201800180

  日期：2018.6.21

  In this contribution, the new dynamic nonlinear effect in asymmetric catalysis is discussed, manifesting itself in the oxidative kinetic resolution (OKR) of racemic secondary benzylic alcohols and alkyl mandelates with H2O2 in the presence of chiral Mn‐based catalyst, with the apparent selectivity factor (krel) of the resolution being nonconstant over the reaction course. Typically, the initial growth

  在这一贡献中，讨论了不对称催化中的新的动态非线性效应，表现为在手性Mn基催化剂存在下，外消旋仲苄醇和烷基扁桃酸酯与H 2 O 2的氧化动力学拆分（OKR）。在整个反应过程中，分辨率的表观选择性因子（k rel）是非恒定的。通常，k rel的初始增长会在高转换率下变为衰减。在这一贡献中，我们证明了带有仲醇部分的各种底物的氧化动力学拆分，k rel随着底物转化率的提高以不同的方式变化。我们还介绍了不对称自动扩增参与的OKR预测动力学模型。讨论了底物和催化剂结构以及溶剂和添加剂对k rel变化行为的影响。
• The role of conformational flexibility of enzymes in the discrimination between amino acid and ester substrates for the subtilisin-catalyzed reaction in organic solvents
  作者：Keiichi Watanabe、Takashi Yoshida、Shin-ichi Ueji

  DOI：10.1016/j.bioorg.2004.05.001

  日期：2004.12

  substrates for the subtilisin-catalyzed reaction in an organic solvent, the flexibility around the active site and the surface of subtilisin was estimated from the mobility of a spin label bound to subtilisin by ESR spectroscopy. Many studies on enzyme flexibility focus on the active site. Both the surface and active site flexibility play an important role in the enantioselectivity enhancement of the enzyme-catalyzed

  为了研究枯草杆菌蛋白酶的构象柔韧性如何影响其区分在有机溶剂中枯草杆菌蛋白酶催化反应的对映体氨基酸和酯底物的能力，通过旋转的迁移率估算了活性中心和枯草杆菌蛋白酶表面的柔韧性ESR光谱法将与枯草杆菌蛋白酶结合的标记。关于酶柔韧性的许多研究都集中在活性位点上。表面和活性位点的柔韧性在酶催化反应的对映选择性增强中都起着重要作用。然而，发现在氨基酸和酯底物之间观察到的对映选择性的不同行为可能与表面周围的柔韧性而不是枯草杆菌蛋白酶活性位点的柔韧性有关。换一种说法，对于酯底物，由于存在添加剂如DMSO而引起的构象变化引起的枯草杆菌蛋白酶表面周围更大的柔韧性对于增强对映选择性是必不可少的。每个对映体底物的Michaelis-Menten动力学参数也支持该模型。我们的发现为有机溶剂中酶催化反应的对映异构体拆分提供了深入的对映选择性的见解。
• Methods and compositions for preventing opioid abuse
  申请人：Waterville Valley Technologies, Inc.

  公开号：US10226456B2

  公开（公告）日：2019-03-12

  Abuse-resistant opioid compounds, drug delivery systems, pharmaceutical compositions comprising an opioid covalently bound to a chemical moiety are provided. Methods of delivering an active ingredient to a subject and methods of preventing opioid abuse are also provided.

  提供了抗滥用阿片类化合物、给药系统、药物组合物，其中包含与化学分子共价结合的阿片类药物。此外，还提供了向受试者输送活性成分的方法和防止滥用阿片类药物的方法。
• Enantioselective α-Hydroxylation of 2-Arylacetic Acid Derivatives and Buspirone Catalyzed by Engineered Cytochrome P450 BM-3
  作者：Marco Landwehr、Lisa Hochrein、Christopher R. Otey、Alex Kasrayan、Jan-E. Bäckvall、Frances H. Arnold

  DOI：10.1021/ja061261x

  日期：2006.5.1

  Here we report that an engineered microbial cytochrome P450 BM-3 (CYP102A subfamily) efficiently catalyzes the alpha-hydroxylation of phenylacetic acid esters. This P450 BM-3 variant also produces the authentic human metabolite of buspirone, R-6-hydroxybuspirone, with 99.5% ee.