(Z)-(4R,5R,6R)-5-((tert-butyldimethylsilyl)oxy)-4,6-dimethyl-7-oxo-hept-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester | 217026-01-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (Z)-(4R,5R,6R)-5-((tert-butyldimethylsilyl)oxy)-4,6-dimethyl-7-oxo-hept-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester
• 英文别名: [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] (Z,4R,5R,6R)-5-[tert-butyl(dimethyl)silyl]oxy-4,6-dimethyl-7-oxohept-2-enoate
• CAS: 217026-01-2
• 化学式: C₃₁H₅₀O₄Si
• 分子量: 514.821
• InChiKey: WHFCSKYUISAYRO-BVMXEGOVSA-N

物化性质

• 沸点：
  552.4±50.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.73
• 重原子数：
  36
• 可旋转键数：
  12
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (Z)-(4R,5R,6R)-5-((tert-butyldimethylsilyl)oxy)-4,6-dimethyl-7-oxo-hept-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester 在 palladium on activated charcoal 氢气 作用下， 25.0 ℃ 、101.32 kPa 条件下， 以86%的产率得到(4R,5R,6R)-5-(tert-Butyl-dimethyl-silanyloxy)-4,6-dimethyl-7-oxo-heptanoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenyl-ethyl)-cyclohexyl ester
  参考文献：
  名称：

  Synthetic Applications of Asymmetric Horner-Wadsworth-Emmons Condensations: Approaches to Marine Natural Products

  摘要：

  DOI：

  10.1080/10426509908546208
• 作为产物：
  描述：

  Xylitol, 2,4-dideoxy-3-O-[(1,1-dimethylethyl)dimethylsilyl]-2,4-dimethyl- 在 草酰氯 、 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 3.5h， 生成 (Z)-(4R,5R,6R)-5-((tert-butyldimethylsilyl)oxy)-4,6-dimethyl-7-oxo-hept-2-enoic acid (1R,2S,5R)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl ester
  参考文献：
  名称：

  Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with meso-Dialdehydes

  摘要：

  Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphsnate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction depended on the structure of the phosphonate (i.e., the alkyl group R-1 in the phosphoryl unit) and to a certain extent also on the reaction conditions. Furthermore, the nature of the protecting group used on the a-oxygen substituent in dialdehydes 14 influenced the outcome somewhat. By an appropriate choice of reagent and conditions, either (E)- or (Z)-monoaddition products could be obtained geometrically pure and with good to excellent diastereoselectivities, in synthetically useful yields. Analyses of the absolute configurations of the products showed that the (E)-selective reagents (3a-c) and the (Z)-selective phosphonate 3d reacted at opposite enantiotopic carbonyl groups in the substrates. A mechanistic model which accounts for the products formed is presented.

  DOI：

  10.1021/jo981102z

文献信息

• Reagent Control of Geometric Selectivity and Enantiotopic Group Preference in Asymmetric Horner−Wadsworth−Emmons Reactions with <i>meso</i>-Dialdehydes
  作者：Joshua S. Tullis、Lauri Vares、Nina Kann、Per-Ola Norrby、Tobias Rein

  DOI：10.1021/jo981102z

  日期：1998.11.1

  Results from asymmetric Horner-Wadsworth-Emmons reactions between chiral phosphsnate reagents 3a-d, which contain (1R,2S,5R)-8-phenylmenthol as a chiral auxiliary, and meso-dialdehydes 6 and 14 are presented. It was found that both the geometric selectivities and the levels of asymmetric induction depended on the structure of the phosphonate (i.e., the alkyl group R-1 in the phosphoryl unit) and to a certain extent also on the reaction conditions. Furthermore, the nature of the protecting group used on the a-oxygen substituent in dialdehydes 14 influenced the outcome somewhat. By an appropriate choice of reagent and conditions, either (E)- or (Z)-monoaddition products could be obtained geometrically pure and with good to excellent diastereoselectivities, in synthetically useful yields. Analyses of the absolute configurations of the products showed that the (E)-selective reagents (3a-c) and the (Z)-selective phosphonate 3d reacted at opposite enantiotopic carbonyl groups in the substrates. A mechanistic model which accounts for the products formed is presented.
• Synthetic Applications of Asymmetric Horner-Wadsworth-Emmons Condensations: Approaches to Marine Natural Products
  作者：Joshua S. Tullis、Paul Helquist、Tobias Rein

  DOI：10.1080/10426509908546208

  日期：1999.1.1