methyl 2-benzyloxy-3-methylbutanoate | 110351-27-4

• 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: methyl 2-benzyloxy-3-methylbutanoate
• 英文别名: Methyl 3-methyl-2-phenylmethoxybutanoate
• CAS: 110351-27-4
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: AQWLSBIWGSPJKL-UHFFFAOYSA-N

物化性质

• 沸点：
  305.6±17.0 °C(Predicted)
• 密度：
  1.032±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 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：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-benzyloxy-3-methylbutanoate 在 2,2,6,6-四甲基哌啶 、 N-溴代丁二酰亚胺(NBS) 、 lithium aluminium tetrahydride 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 生成 (2E,4R*)-Methyl 2-(N-benzoylamino)-4-(benzyloxy)-3-bromo-5-methyl-2-hexenoate
  参考文献：
  名称：

  Stereoselective bromination of dehydroamino acids with controllable retention or inversion of olefin configuration

  摘要：

  Dehydroamino acid esters react with brominating reagents to produce syn-a-bromo imines as the major products, which undergo tautomerization to mixtures of the diastereomeric (E)- and (Z)-beta-bromo-alpha,beta-dehydroamino acids upon treatment with base. Herein, we examine the characteristics of dehydroamino acid substrates 1 that affect both the diastereofacial selectivity of the bromination and the configuration of the resulting olefin product(s) 3. In these studies, we demonstrate E- and Z-diastereoselectivity for this reaction using kinetic and thermodynamic reaction conditions. Z-Vinyl bromides were shown to be the thermodynamically more stable products and were formed from the kinetic E-isomers by DABCO-induced isomerization. High levels of kinetic E-selectivity were obtained by treatment of the intermediate alpha-bromo imines with hindered amine bases such as 2,2,6,6-tetramethylpiperidine or sodium hexamethyldisilazide. The reaction conditions detailed herein allow for the stereodivergent preparation of both E- and Z-vinyl bromide products from either diastereomeric E- or Z-olefin starting material with useful levels of diastereoselectivity.

  DOI：

  10.1021/jo00068a047
• 作为产物：
  描述：

  2-羟基-3-甲基丁酸 在 四丁基碘化铵 、 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 0.75h， 生成 methyl 2-benzyloxy-3-methylbutanoate
  参考文献：
  名称：

  Stereoselective bromination of dehydroamino acids with controllable retention or inversion of olefin configuration

  摘要：

  Dehydroamino acid esters react with brominating reagents to produce syn-a-bromo imines as the major products, which undergo tautomerization to mixtures of the diastereomeric (E)- and (Z)-beta-bromo-alpha,beta-dehydroamino acids upon treatment with base. Herein, we examine the characteristics of dehydroamino acid substrates 1 that affect both the diastereofacial selectivity of the bromination and the configuration of the resulting olefin product(s) 3. In these studies, we demonstrate E- and Z-diastereoselectivity for this reaction using kinetic and thermodynamic reaction conditions. Z-Vinyl bromides were shown to be the thermodynamically more stable products and were formed from the kinetic E-isomers by DABCO-induced isomerization. High levels of kinetic E-selectivity were obtained by treatment of the intermediate alpha-bromo imines with hindered amine bases such as 2,2,6,6-tetramethylpiperidine or sodium hexamethyldisilazide. The reaction conditions detailed herein allow for the stereodivergent preparation of both E- and Z-vinyl bromide products from either diastereomeric E- or Z-olefin starting material with useful levels of diastereoselectivity.

  DOI：

  10.1021/jo00068a047

文献信息

• Asymmetric Synthesis of .BETA.-Hydroxy Acid via Stereoselective Dirhodium(II)-Catalyzed C-H Insertion of .ALPHA.-Alkoxydiazoketone.
  作者：Takayuki Yakura、Takeshi Tanaka、Masazumi Ikeda、Jun'ichi Uenishi

  DOI：10.1248/cpb.51.471

  日期：——

  A new methodology for the asymmetric synthesis of beta-hydroxy acid was developed. Dirhodium(II)-catalyzed C-H insertion of alpha-alkoxydiazoketone (3), which was prepared from primary alkyl halide (1) and readily available chiral alpha-hydroxy acid (2), gave stereoselectively 2,5-cis-disubstituted 3(2H)-furanone (4). The Baeyer-Villiger reaction of 4 followed by treatment with an acid afforded chiral

  开发了一种不对称合成β-羟基酸的新方法。由伯烷基卤化物（1）和易于获得的手性α-羟基酸（2）制备的二烷基吡啶鎓（II）催化CH插入的α-烷氧基重氮酮（3），产生了立体选择性的2,5-顺式二取代的3（2H） ）-呋喃酮（4）。4的Baeyer-Villiger反应，然后用酸处理，得到具有高光学纯度的手性β-羟基酸（6）。
• DIAZONAMIDE ANALOGS WITH IMPROVED SOLUBILITY
  申请人：HANSON Gunnar James

  公开号：US20090163446A1

  公开（公告）日：2009-06-25

  Diazonamide A analogs, and the salts, esters and conjugates thereof, having improved aqueous solubility are provided. Also provided are pharmaceutical compositions, and methods for preparing and using such compounds and compositions for the treatment of proliferative diseases.

  提供了具有改善水溶性的Diazonamide A类似物，以及其盐、酯和共轭物。还提供了用于治疗增殖性疾病的药物组合物，以及制备和使用这些化合物和组合物的方法。
• Enzyme-mediated asymmetric hydrolysis of α-benzyloxycarboxylic esters
  作者：Yasuo Kato、Hiromichi Ohta、Gen-ichi Tsuchihashi

  DOI：10.1016/s0040-4039(00)95353-x

  日期：1987.1
• KATO YASUO; OHTA HIROMICHI; TSUCHIHASHI GEN-ICHI, TETRAHEDRON LETT., 28,(1987) N 12, 1303-1306
  作者：KATO YASUO、 OHTA HIROMICHI、 TSUCHIHASHI GEN-ICHI

  DOI：——

  日期：——
• [EN] DIAZONAMIDE ANALOGS WITH IMPROVED SOLUBILITY<br/>[FR] ANALOGUES DE DIAZONAMIDE AVEC UNE SOLUBILITÉ AMÉLIORÉE
  申请人：JOYANT PHARMACEUTICALS INC

  公开号：WO2009086170A1

  公开（公告）日：2009-07-09

  Diazonamide A analogs, and the salts, esters and conjugates thereof, having improved aqueous solubility are provided. Also provided are pharmaceutical compositions, and methods for preparing and using such compounds and compositions for the treatment of proliferative diseases.