(S)-3-Isopropylidene-4-(1-methoxy-1-methyl-ethyl)-cyclopentane-1,1-dicarboxylic acid dimethyl ester | 213531-64-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (S)-3-Isopropylidene-4-(1-methoxy-1-methyl-ethyl)-cyclopentane-1,1-dicarboxylic acid dimethyl ester
• 英文别名: dimethyl (3S)-3-(2-methoxypropan-2-yl)-4-propan-2-ylidenecyclopentane-1,1-dicarboxylate
• CAS: 213531-64-7
• 化学式: C₁₆H₂₆O₅
• 分子量: 298.379
• InChiKey: HCMDPXAUPBPFOH-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-3-Isopropylidene-4-(1-methoxy-1-methyl-ethyl)-cyclopentane-1,1-dicarboxylic acid dimethyl ester 在 臭氧 、 二甲基硫 作用下， 生成 (R)-3-(1-Methoxy-1-methyl-ethyl)-4-oxo-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Asymmetric Intramolecular Radical Vinylation Using Enantiopure Sulfoxides as Temporary Chiral Auxiliaries

  摘要：

  A very diastereoselective addition-elimination sequence affords cyclopentane derivatives in high enantiomeric purities. The enantiopure sulfoxide unit serves as a very efficient temporary chiral auxiliary in this tandem reaction. Interestingly, the presence of the MAD Lewis acid totally reverses the stereochemical outcome of this reaction. Several determining parameters of this sequence have been investigated: the substitution of the vinyl sulfoxide moiety, the nature of the prochiral radical, the aromatic substituent of the sulfoxide group, the tether, and the role played by different Lewis acids.

  DOI：

  10.1021/ja992818u
• 作为产物：
  描述：

  (S)-1-bromo-3-methyl-2-p-tolylsulfinyl-2-butene 在 三乙基硼 、 氧气 、 三正丁基氢锡 、 甲铝双(2,6-二叔丁基-4-苯甲醚) 、 sodium hydride 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.0h， 生成 (S)-3-Isopropylidene-4-(1-methoxy-1-methyl-ethyl)-cyclopentane-1,1-dicarboxylic acid dimethyl ester
  参考文献：
  名称：

  Radical Cyclization/β-Elimination Tandem Reactions: Enantiopure Sulfoxides as Temporary Chiral Auxiliaries

  摘要：

  Alkylidene-substituted cyclopentane derivatives are formed in high enantiomeric purity by the reaction shown below. A highly diastereoselective radical cyclization is followed by elimination of a β-sulfinyl radical. Interestingly, the addition of the Lewis acid methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) totally reverses the stereochemical outcome of the reaction. E=CO2 Me.

  DOI：

  10.1002/(sici)1521-3773(19980817)37:15<2116::aid-anie2116>3.0.co;2-l

文献信息

• Radical Cyclization/β-Elimination Tandem Reactions: Enantiopure Sulfoxides as Temporary Chiral Auxiliaries
  作者：Emmanuel Lacôte、Bénédicte Delouvrié、Louis Fensterbank、Max Malacria

  DOI：10.1002/(sici)1521-3773(19980817)37:15<2116::aid-anie2116>3.0.co;2-l

  日期：1998.8.17

  Alkylidene-substituted cyclopentane derivatives are formed in high enantiomeric purity by the reaction shown below. A highly diastereoselective radical cyclization is followed by elimination of a β-sulfinyl radical. Interestingly, the addition of the Lewis acid methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) totally reverses the stereochemical outcome of the reaction. E=CO2 Me.
• Asymmetric Intramolecular Radical Vinylation Using Enantiopure Sulfoxides as Temporary Chiral Auxiliaries
  作者：Bénédicte Delouvrié,、Louis Fensterbank、Emmanuel Lacôte、Max Malacria

  DOI：10.1021/ja992818u

  日期：1999.12.1

  A very diastereoselective addition-elimination sequence affords cyclopentane derivatives in high enantiomeric purities. The enantiopure sulfoxide unit serves as a very efficient temporary chiral auxiliary in this tandem reaction. Interestingly, the presence of the MAD Lewis acid totally reverses the stereochemical outcome of this reaction. Several determining parameters of this sequence have been investigated: the substitution of the vinyl sulfoxide moiety, the nature of the prochiral radical, the aromatic substituent of the sulfoxide group, the tether, and the role played by different Lewis acids.