(+)-2-phenylapopinene | 156408-12-7

• 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: (+)-2-phenylapopinene
• 英文别名: (1S,5R)-6,6-dimethyl-2-phenylbicyclo[3.1.1]hept-2-ene
• CAS: 156408-12-7
• 化学式: C₁₅H₁₈
• 分子量: 198.308
• InChiKey: SYRDENIJTJYALZ-TZMCWYRMSA-N

物化性质

• 沸点：
  279.4±7.0 °C(Predicted)
• 密度：
  0.995±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (+)-2-phenylapopinene 在 9-borabicyclo[3.3.1]nonane dimer 、 双氧水 作用下， 生成 (1R,2S,3R,5S)-6,6-Dimethyl-2-phenyl-bicyclo[3.1.1]heptan-3-ol
  参考文献：
  名称：

  Hydroboration. 94. Rates of Hydroboration of 2-Organylapopinenes with 9-Borabicyclo[3.3.1]nonane, Providing B-(2-Organylapoisopinocampheyl)-9-borabicyclo[3.3.1]nonanes, Potentially Valuable for the Asymmetric Reduction of Prochiral Ketones

  摘要：

  Five representative enantiomerically pure, hindered terpenes, derived from a-pinene, namely 8-organylapopinenes (2-R-apopinenes, R = Et, Pr, i-Bu, Ph, and i-Pr) have been treated with 9-borabicyclo[3.3.1]nonane (9-BBN) in a 1:1 molar ratio in THF at 24 degrees C and the rate of hydroboration followed. Increasing the bulk of the 2-R group from the 2-methyl of alpha-pinene (Ipc, 2-methylapopinene) to 8-ethyl-(Eap), to 2-propyl-(Prap), to 2-isobutyl-(i-Bap), to 2-phenyl-(Pap), and to 2-isopropyl-(i-Prap) significantly lowers the rate of hydroboration with 9-BBN. Thus, the rate of hydroboration of alpha-pinene with 9-BBN is faster than the rates for the 2-R-apopinenes studied. The sterically bulkier 2-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes reveal a significantly slower rate of hydroboration with 9-BBN. At an elevated temperature, 65 degrees C, the reaction of 9-BBN (1.0 equiv) with a slight excess of optically pure 2-isobutyl- and 2-phenylapopinenes (1.10-1.20 equiv), under neat conditions, is facilitated to provide the desired B-(2-organylapoisopinocampheyl)-9-borabicyclo[3.3.1]nonanes (2-organyl = isobutyl- and phenyl) in quantitative yield. Unfortunately, this synthesis failed for 2-isopropylapopinene. Fortunately, an indirect synthesis proved satisfactory. Treatment of enantiomerically pure (2-isopropylapoisopinocampheyl)borane, i-PrapBH(2), conveniently synthesized from 2-isopropylapopinene, and 1,5-cyclooctadiene (1,5-COD), provided, after thermal isomerization, the desired 1:1 adduct [B-(2-Rap)-9-BBN; 2-Rap = 2-isopropylapoisopinyl skeleton] in quantitative yield. Consequently, five of the 2-R-apopinenes, R = Et, Pr, i-Bu, Ph, and i-Pr, have been successfully converted into the corresponding B-(2-Rap)-9-BBN derivatives.

  DOI：

  10.1021/jo9617169
• 作为产物：
  描述：

  6,6-dimethyl-2-phenylbicyclo[3.1.1]heptan-2-ol 在 三氯氧磷 作用下， 以 吡啶 为溶剂， 反应 24.0h， 以75%的产率得到(+)-2-phenylapopinene
  参考文献：
  名称：

  不同结构改性的二醇对手性（-）-戊二醇甲基硼酸酯的酯交换反应的研究

  摘要：

  通过各种结构改性的二醇，通过1 H NMR研究了手性（-）-with烷二醇甲基硼酸酯的酯交换反应，以了解影响该硼酸酯异常稳定性的因素，并找到从其甲基硼酸酯中回收pin二醇的方法。在所有情况下，使反应进行到平衡。初步实验确实显示了一些令人鼓舞的结果（pin烷二醇的取代率高达40-53％）。在基于环戊烷的 顺式 -1,2-二醇中， 内 -2-苯基 -exo ， exo -2,3-降冰片烷二醇似乎是取代pin烷二醇最有效的二醇（38％）。在基于pin烷的二醇的情况下，使用2-乙基-6,6-二甲基双环[3.1.1]庚烷- 顺式 -2,3-二醇（53％）可获得最佳结果 。有趣的是，观察到与2-苯基-6,6-二甲基双环[3.1.1]庚烷- 顺式 -2,3-二醇的酯交换反应 仅在4天后即可产生50％的转化率，而前一个二醇则需要24天达到平衡。

  DOI：

  10.1007/s00706-007-0681-7

文献信息

• Three‐Component Difunctionalization of Cyclohexenyl Triflates: Direct Access to Versatile Cyclohexenes via Cyclohexynes
  作者：Seoyoung Cho、E. J. McLaren、Qiu Wang

  DOI：10.1002/anie.202109482

  日期：2021.12.6

  dicarbofunctionalization, aminohalogenation and aminocarbonation of readily available cyclohexenyl triflates, via strained cyclic alkyne intermediates generated in situ. The importance and utility of this method is exemplified by the modularity of this approach and the ease in which even highly complex polycyclic scaffolds can be accessed in one step.

  我们报告了一种有效且灵活的方法，通过原位生成的应变环炔中间体，实现易于获得的环己烯基三氟甲磺酸酯的碳卤化、双碳功能化、氨基卤化和氨基碳化。这种方法的重要性和实用性体现在这种方法的模块化以及即使高度复杂的多环支架也可以一步访问的容易性。
• Hydroboration of Terpenes. 11. Convenient Method for Upgrading 2-Organylapopinenes to High Optical Purity by Reaction of 2-Organylapoisopinocampheylboranes with Suitable Dienes Followed by Displacement with Acetaldehyde
  作者：Herbert C. Brown、Ulhas P. Dhokte

  DOI：10.1021/jo00097a065

  日期：1994.9