ethyl 3-[(tert-butyl)dimethylsiloxy]-2,2-difluoro-4-phenylbutanoate | 330801-23-5

• 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: ethyl 3-[(tert-butyl)dimethylsiloxy]-2,2-difluoro-4-phenylbutanoate
• CAS: 330801-23-5
• 化学式: C₁₈H₂₈F₂O₃Si
• 分子量: 358.501
• InChiKey: QAOTZAGBSJSGFQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.82
• 重原子数：
  24.0
• 可旋转键数：
  7.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.61
• 拓扑面积：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  ethyl 3-[(tert-butyl)dimethylsiloxy]-2,2-difluoro-4-phenylbutanoate 在 Me2Cu(CN)Li2*2LiBr 、 二异丁基氢化铝 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 、 乙腈 为溶剂， 反应 0.25h， 生成 (Z)-5-(tert-Butyl-dimethyl-silanyloxy)-4-fluoro-6-phenyl-hex-3-enoic acid tert-butyl ester
  参考文献：
  名称：

  Synthesis of (Z)-fluoroalkene dipeptide isosteres utilizing organocopper-mediated reduction of γ,γ-difluoro-α,β-enoates

  摘要：

  gamma,gamma -Difluoro-alpha,beta -enoates are reduced with organocopper reagents to afford the corresponding gamma -fluoro-beta,gamma -enoates. This organocopper-mediated reduction was applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01924-9
• 作为产物：
  描述：

  叔丁基二甲硅基三氟甲磺酸酯 、 ethyl 2,2-difluoro-3-hydroxy-4-phenylbutanoate 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以68%的产率得到ethyl 3-[(tert-butyl)dimethylsiloxy]-2,2-difluoro-4-phenylbutanoate
  参考文献：
  名称：

  SmI₂-Mediated Reduction of γ,γ-Difluoro-α,β-enoates with Application to the Synthesis of Functionalized (Z)-Fluoroalkene-Type Dipeptide Isosteres

  摘要：

  A samarium diiodide (SmI2)-mediated reduction of gamma,gamma-difluoro-alpha,beta-enoates (15, 29, and 34) was successfully applied to the synthesis of (Z)-fluoroalkene dipeptide isosteres (23, 30, and 35), which have served as potential dipeptide mimetics. Reduction of the gamma,gamma-difluoro-alpha,beta-enoates by SmI2 proceeded via successive two-electron transfers to form dienolate species which upon kinetically controlled trapping with t-BuOH yielded Xaa-Gly-type fluoroalkene isosteres exemplified by 23, 30, and 35. Replacement of the t-BuOH kinetic trapping agent with aldehydes or ketones provided access to a-substituted fluoroalkene isosteres (43 and 45) through aldol reactions of Sm-dienolates with the carbonyl compounds. Of particular note, the use of the SmI2-HCHO reagent system with chiral enoate 34 provided D-Phe-psi[(Z)-CF=CH]-D/L-Ser isosteres (45), which could be converted to enantiomerically pure isosteres (49-52) that bore a variety of side chain functionalities at the a-position. This was achieved by a sequence of manipulations consisting of beta-lactone formation followed by chromatographic separation and ring-opening with soft nucleophiles. Included in the present work is the first utilization of a Rh-catalyzed Reformatsky reaction of chiral imines for the stereoselective preparation of alpha,alpha-difluoro-beta-amino acid derivatives (28 and 33). The appropriate choice of reagents (carbonyl compounds for kinetic trapping or ring-opening nucleophiles and imines for Reformatsky reactions) allows the presented methodology to yield various fluoroalkene isosteres possessing a wide range of side chain functionalities.

  DOI：

  10.1021/jo035709d