methyl β,β-difluoro-α-trimethylsilyloxyacrylate | 491612-52-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: methyl β,β-difluoro-α-trimethylsilyloxyacrylate
• 英文别名: methyl 3,3-difluoro-2-trimethylsilyloxyacrylate；methyl 3,3-trifluoro-2-trimethylsiloxyacrylate；2-Propenoic acid, 3,3-difluoro-2-[(trimethylsilyl)oxy]-, methyl ester；methyl 3,3-difluoro-2-trimethylsilyloxyprop-2-enoate
• CAS: 491612-52-3
• 化学式: C₇H₁₂F₂O₃Si
• 分子量: 210.253
• InChiKey: GPHHDRRTMUGMDM-UHFFFAOYSA-N

物化性质

• 沸点：
  133.4±40.0 °C(Predicted)
• 密度：
  1.085±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.12
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl β,β-difluoro-α-trimethylsilyloxyacrylate 在 溴 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以64%的产率得到methyl 3-bromo-3,3-difluoropyruvate
  参考文献：
  名称：

  Preparation and synthetic application of methyl β,β-difluoro-α-trimethylsilyloxyacrylate: a fluoride ion-promoted desilylative-defluorination route

  摘要：

  Catalytic amount of TBAT (0.2 mol %) promoted desilylation and subsequent defluorination of ketene silyl acetal of methyl O-trimethylsilyltrifluorolactate, affording methyl beta,beta-difluoro-alpha-trimethylsilyloxyacrylate in 95% yield of which reaction with electrophiles provided methyl beta-substituted-beta,beta-difluoropyruvate in good yields. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.07.049
• 作为产物：
  描述：

  1-methoxy-1-(trimethylsilyloxy)-2-(trifluoromethyl)-2-(trimethylsilyloxy)ethene 在 四丁基二氟三苯硅酸铵 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以95%的产率得到methyl β,β-difluoro-α-trimethylsilyloxyacrylate
  参考文献：
  名称：

  Preparation and synthetic application of methyl β,β-difluoro-α-trimethylsilyloxyacrylate: a fluoride ion-promoted desilylative-defluorination route

  摘要：

  Catalytic amount of TBAT (0.2 mol %) promoted desilylation and subsequent defluorination of ketene silyl acetal of methyl O-trimethylsilyltrifluorolactate, affording methyl beta,beta-difluoro-alpha-trimethylsilyloxyacrylate in 95% yield of which reaction with electrophiles provided methyl beta-substituted-beta,beta-difluoropyruvate in good yields. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.07.049

文献信息

• Preparation and Synthetic Application of a Novel Ketene Silyl Acetal of Methyl Trifluoropyruvate
  作者：Go Takikawa、Toshimasa Katagiri、Kenji Uneyama

  DOI：10.1021/jo051242q

  日期：2005.10.1

  A novel trifluoromethyl ketene silyl acetal (4) of methyl trifluoropyruvate (1) was prepared in 82% yield by metal Mg reduction in a (TMS)Cl/THF system. Subsequent carbon−carbon bond formation such as Mukaiyama aldol, Michael addition, and other nucleophilic reactions of 4 at the trifluoromethylated carbon with various electrophiles gave various coupling products in high yields.

  通过在（TMS）Cl / THF系统中还原金属Mg，以82％的收率制备了三氟丙酮酸甲酯（1）的新型三氟甲基乙烯酮甲硅烷基缩醛（4）。随后的碳-碳键形成，例如Mukaiyama aldol，Michael加成，以及在三氟甲基化碳上与各种亲电试剂进行的其他4亲核反应，均以高收率得到了各种偶联产物。
• Methyl 3,3-difluoro-2-trimethylsilyloxyacrylate: preparation and Mukaiyama-type aldol condensation as a novel route to β,β-difluoro-α-keto ester derivatives
  作者：Biao Jiang、Xiaobing Zhang、Guoqiang Shi

  DOI：10.1016/s0040-4039(02)01504-6

  日期：2002.9

  Mukaiyama-type aldol condensation of arylaldehyde acetals occurs smoothly with methyl 3,3-difluoro-2-trimethylsilyloxyacrylate (derived from ethyl 3,3-difluoro-2-benzoylacrylate) when catalyzed by a Lewis acid, allowing preparation of 4-alkyloxy-3,3-difluoro-2-keto esters in high yields.

  路易斯酸催化下，与3,3-二氟-2-三甲基甲硅烷基氧基丙烯酸甲酯（衍生自3,3-二氟-2-苯甲酰基丙烯酸乙酯）形成的Mukaiyama型醛缩醛醛醇缩合反应顺利进行，从而制备了4-烷氧基-3 ，3-二氟-2-酮酯的收率很高。
• Preparation and synthetic application of methyl β,β-difluoro-α-trimethylsilyloxyacrylate: a fluoride ion-promoted desilylative-defluorination route
  作者：Go Takikawa、Kouzou Toma、Kenji Uneyama

  DOI：10.1016/j.tetlet.2006.07.049

  日期：2006.9

  Catalytic amount of TBAT (0.2 mol %) promoted desilylation and subsequent defluorination of ketene silyl acetal of methyl O-trimethylsilyltrifluorolactate, affording methyl beta,beta-difluoro-alpha-trimethylsilyloxyacrylate in 95% yield of which reaction with electrophiles provided methyl beta-substituted-beta,beta-difluoropyruvate in good yields. (c) 2006 Elsevier Ltd. All rights reserved.