(-)-(1E,3S,4R)-4-hydroxy-3,5-dimethyl-1-trimethylsilyl-1-hexenyl N,N-diisopropylcarbamate | 678150-32-8

• 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: (-)-(1E,3S,4R)-4-hydroxy-3,5-dimethyl-1-trimethylsilyl-1-hexenyl N,N-diisopropylcarbamate
• 英文别名: [(E,3S,4R)-4-hydroxy-3,5-dimethyl-1-trimethylsilylhex-1-enyl] N,N-di(propan-2-yl)carbamate
• CAS: 678150-32-8
• 化学式: C₁₈H₃₇NO₃Si
• 分子量: 343.582
• InChiKey: JLLWWDCGWROCBN-XRFBDRIGSA-N

物化性质

• 沸点：
  412.5±45.0 °C(Predicted)
• 密度：
  0.941±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.66
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-(1E,3S,4R)-4-hydroxy-3,5-dimethyl-1-trimethylsilyl-1-hexenyl N,N-diisopropylcarbamate 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 22.0h， 以86%的产率得到(1Z)-(3R*,4S*)-4-hydroxy-3,5-dimethylhex-1-enyl N,N-diisopropylcarbamate
  参考文献：
  名称：

  Highly Enantioenriched Homoenolate Reagents by Asymmetric γ-Deprotonation of Achiral 1-Silyl-Substituted 1-Alkenyl Carbamates

  摘要：

  1-Trimethylsilyl-1-alkenyl carbamates 1 are deprotonated by n-butyllithium/(-)-sparteine (2) with a high degree of enantiotopic differentiation in the gamma-position to form the enantiomerically enriched allyllithium derivatives 3. Trapping these with several electrophiles proceeds stereospecifically in an anti-S-E' or syn-S-E' substitution to form products 4 or ent-4, respectively. Compounds 3a (R = Me) and 3b (R = Ph) exhibit toward carbonyl electrophiles opposite senses of almost complete stereospecificity, thus for 3b(.)2 the involvement of a eta(3)-complex is suggested.

  DOI：

  10.1021/ol0364677
• 作为产物：
  描述：

  (E)-but-2-enyl N,N-diisopropylcarbamate 在 正丁基锂 、 四甲基乙二胺 、 鹰爪豆碱 作用下， 以 乙醚 、 正己烷 、 甲苯 为溶剂， 反应 23.25h， 生成 (-)-(1E,3S,4R)-4-hydroxy-3,5-dimethyl-1-trimethylsilyl-1-hexenyl N,N-diisopropylcarbamate
  参考文献：
  名称：

  Highly Enantioenriched Homoenolate Reagents by Asymmetric γ-Deprotonation of Achiral 1-Silyl-Substituted 1-Alkenyl Carbamates

  摘要：

  1-Trimethylsilyl-1-alkenyl carbamates 1 are deprotonated by n-butyllithium/(-)-sparteine (2) with a high degree of enantiotopic differentiation in the gamma-position to form the enantiomerically enriched allyllithium derivatives 3. Trapping these with several electrophiles proceeds stereospecifically in an anti-S-E' or syn-S-E' substitution to form products 4 or ent-4, respectively. Compounds 3a (R = Me) and 3b (R = Ph) exhibit toward carbonyl electrophiles opposite senses of almost complete stereospecificity, thus for 3b(.)2 the involvement of a eta(3)-complex is suggested.

  DOI：

  10.1021/ol0364677

文献信息

• Highly Enantioenriched Homoenolate Reagents by Asymmetric γ-Deprotonation of Achiral 1-Silyl-Substituted 1-Alkenyl Carbamates
  作者：Jenny Reuber、Roland Fröhlich、Dieter Hoppe

  DOI：10.1021/ol0364677

  日期：2004.3.1

  1-Trimethylsilyl-1-alkenyl carbamates 1 are deprotonated by n-butyllithium/(-)-sparteine (2) with a high degree of enantiotopic differentiation in the gamma-position to form the enantiomerically enriched allyllithium derivatives 3. Trapping these with several electrophiles proceeds stereospecifically in an anti-S-E' or syn-S-E' substitution to form products 4 or ent-4, respectively. Compounds 3a (R = Me) and 3b (R = Ph) exhibit toward carbonyl electrophiles opposite senses of almost complete stereospecificity, thus for 3b(.)2 the involvement of a eta(3)-complex is suggested.