ethyl 2-[(4S,5R,6R)-5,6-dimethyl-2-phenyl-1,3-dioxan-4-yl]acetate | 342900-89-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: ethyl 2-[(4S,5R,6R)-5,6-dimethyl-2-phenyl-1,3-dioxan-4-yl]acetate
• 英文别名: ethyl 2-((2S,4R,5S,6S)-5,6-dimethyl-2-phenyl-1,3-dioxan-4-yl)acetate；ethyl 2-[(2S,4R,5S,6S)-5,6-dimethyl-2-phenyl-1,3-dioxan-4-yl]acetate
• CAS: 342900-89-4
• 化学式: C₁₆H₂₂O₄
• 分子量: 278.348
• InChiKey: WDWNEMUAYQPCNS-GMZLATJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2-[(4S,5R,6R)-5,6-dimethyl-2-phenyl-1,3-dioxan-4-yl]acetate 在 palladium dihydroxide 六甲基磷酰三胺 、 2,6-二叔丁基-4-甲基吡啶 、 氢气 、 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， -78.0~23.0 ℃ 、101.33 kPa 条件下， 反应 56.0h， 生成 (3R,4R,5R,6S)-3,4,5,6-tetrahydro-3,5,6-trimethyl-4-(triethylsilyloxy)-2H-pyran-2-ol
  参考文献：
  名称：

  Asymmetric Synthesis of the C(33) - C(37) Fragment of Amphotericin B

  摘要：

  We have devised an expeditious. efficient, asymmetric synthesis of the C(33)-C(37) fragment of amphotericin B that proceeds in 14 steps and 16% overall yield from tiglic aldehyde ((E)-2-methylbut-2-enal) with complete stereocontrol. The route described herein relies on the application of recently developed methods in catalytic asymmetric synthesis for stereocontrol through enantio- and diastereoselective functionalization of a substituted sorbate derivative.

  DOI：

  10.1002/1522-2675(20010321)84:3<613::aid-hlca613>3.0.co;2-4
• 作为产物：
  描述：

  (E)-ethyl 3-((4S,5R)-4,5-dimethyl-2-oxo-1,3-dioxolan-4-yl)acrylate 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 甲酸 、 potassium tert-butylate 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 4.58h， 生成 ethyl 2-[(4S,5R,6R)-5,6-dimethyl-2-phenyl-1,3-dioxan-4-yl]acetate
  参考文献：
  名称：

  De Novo Synthesis of 2-Substituted syn-1,3-Diols via an Iterative Asymmetric Hydration Strategy

  摘要：

  The enantioselective syntheses of several protected 4-substituted syn-3,5-dihydroxy carboxylic esters have been achieved from the corresponding achiral (E,E)- or (E,Z)-1,3-dienoates. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to form gamma-substituted delta-hydroxy-1-enoates. The resulting delta-hydroxy-1-enoates are subsequently converted into benzylidene-protected 4-substituted syn-3,5-dihydroxy carboxylic esters in one step. The benzylidene-protected 3,5-dihydroxy carboxylic esters are produced in good overall yields (20-54%) and high enantiomeric excess (73- 97% ee).

  DOI：

  10.1021/jo061200h

文献信息

• Asymmetric Synthesis of the C(33) - C(37) Fragment of Amphotericin B
  作者：Joakim Tholander、Erick M. Carreira

  DOI：10.1002/1522-2675(20010321)84:3<613::aid-hlca613>3.0.co;2-4

  日期：2001.3.21

  We have devised an expeditious. efficient, asymmetric synthesis of the C(33)-C(37) fragment of amphotericin B that proceeds in 14 steps and 16% overall yield from tiglic aldehyde ((E)-2-methylbut-2-enal) with complete stereocontrol. The route described herein relies on the application of recently developed methods in catalytic asymmetric synthesis for stereocontrol through enantio- and diastereoselective functionalization of a substituted sorbate derivative.
• De Novo Synthesis of 2-Substituted <i>syn</i>-1,3-Diols via an Iterative Asymmetric Hydration Strategy
  作者：Md. Moinuddin Ahmed、Matthew S. Mortensen、George A. O'Doherty

  DOI：10.1021/jo061200h

  日期：2006.9.1

  The enantioselective syntheses of several protected 4-substituted syn-3,5-dihydroxy carboxylic esters have been achieved from the corresponding achiral (E,E)- or (E,Z)-1,3-dienoates. The route relies upon an enantio- and regioselective Sharpless dihydroxylation and a palladium-catalyzed reduction to form gamma-substituted delta-hydroxy-1-enoates. The resulting delta-hydroxy-1-enoates are subsequently converted into benzylidene-protected 4-substituted syn-3,5-dihydroxy carboxylic esters in one step. The benzylidene-protected 3,5-dihydroxy carboxylic esters are produced in good overall yields (20-54%) and high enantiomeric excess (73- 97% ee).