(6R)-1-bromo-6-methoxycyclohexene

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (6R)-1-bromo-6-methoxycyclohexene
• 化学式: C₇H₁₁BrO
• 分子量: 191.068
• InChiKey: FPAXROPSIFIQFV-SSDOTTSWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-bromocyclohex-2-en-1-ol 、 碘甲烷 生成 (6R)-1-bromo-6-methoxycyclohexene 、 (S)-(-)-1-bromo-6-methoxycyclohexene
  参考文献：
  名称：

  Sensitivity of Substitution to the Extent of Self-Immolative Chirality Transfer during Reaction Cascades Originating from Squarate Esters

  摘要：

  Reaction cascades induced by the addition to diisopropyl squarate of at least one cycloalkenyl anion possessing an oxygenated leaving group have been examined for the purpose of evaluating the level of chirality transferred to several new stereogenic centers as the original one is destroyed through beta-elimination. A methoxy group alone necessarily resides too far from the bonding sites involved in conrotatory ring closure of the coiled octatetraene intermediate to have a large impact, viz, greater than 22% ee. The situation is considerably improved if a (tert-butyldimethylsilyl)oxy (OTBS) substituent is positioned nearer to this key helical biasing site. The relative rates of ring closure from the two helices of different pitch now become sufficiently different (>100:1) that mechanistic control by OTBS dominates completely, Finally, an example of overwhelming steric bias is detailed (see 30), showing that electrocyclic control can also be achieved in this manner.

  DOI：

  10.1021/jo962182e

文献信息

• Sensitivity of Substitution to the Extent of Self-Immolative Chirality Transfer during Reaction Cascades Originating from Squarate Esters
  作者：Leo A. Paquette、Lung Huang Kuo、Ashton T. Hamme、Rüdiger Kreuzholz、Julien Doyon

  DOI：10.1021/jo962182e

  日期：1997.3.1

  Reaction cascades induced by the addition to diisopropyl squarate of at least one cycloalkenyl anion possessing an oxygenated leaving group have been examined for the purpose of evaluating the level of chirality transferred to several new stereogenic centers as the original one is destroyed through beta-elimination. A methoxy group alone necessarily resides too far from the bonding sites involved in conrotatory ring closure of the coiled octatetraene intermediate to have a large impact, viz, greater than 22% ee. The situation is considerably improved if a (tert-butyldimethylsilyl)oxy (OTBS) substituent is positioned nearer to this key helical biasing site. The relative rates of ring closure from the two helices of different pitch now become sufficiently different (>100:1) that mechanistic control by OTBS dominates completely, Finally, an example of overwhelming steric bias is detailed (see 30), showing that electrocyclic control can also be achieved in this manner.