(1S)-2-异丙基-6,6-二甲基双环[3.1.1]庚-2-烯 | 156327-05-8

• 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
• 中文名称: (1S)-2-异丙基-6,6-二甲基双环[3.1.1]庚-2-烯
• 中文别名: 乙酮1-(1,2,3,4-四氢-2-吡啶基)-(9CI)
• 英文名称: (+)-2-Isopropylapopinene
• 英文别名: Bicyclo[3.1.1]hept-2-ene, 6,6-dimethyl-2-(1-methylethyl)-, (1S)-(9CI)；(1S,5R)-6,6-dimethyl-2-propan-2-ylbicyclo[3.1.1]hept-2-ene
• CAS: 156327-05-8
• 化学式: C₁₂H₂₀
• 分子量: 164.291
• InChiKey: HQZUZTRNTHLWOG-MWLCHTKSSA-N

物化性质

• 沸点：
  197.0±7.0 °C(Predicted)
• 密度：
  0.878±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  (1S)-2-异丙基-6,6-二甲基双环[3.1.1]庚-2-烯 、 alkaline earth salt of/the/ methylsulfuric acid 以 四氢呋喃 为溶剂， 反应 24.0h， 以13%的产率得到9-[(1R,2R,3R,5R)-6,6-dimethyl-2-propan-2-yl-3-bicyclo[3.1.1]heptanyl]-9-borabicyclo[3.3.1]nonane
  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：

  1-(6,6-dimethyl-bicyclo[3.1.1]hept-2-en-2-yl)-ethanol 在 四氯化碳 、 copper(l) iodide 、 三苯基膦 作用下， 反应 17.0h， 生成 (1S)-2-异丙基-6,6-二甲基双环[3.1.1]庚-2-烯
  参考文献：
  名称：

  Hydroboration. 90. Synthesis of 2-Isobutyl- and 2-Isopropylapopinenes. Rates and Stoichiometry of the Hydroboration of 2-Organylapopinenes with Borane-Methyl Sulfide and Borane-Tetrahydrofuran

  摘要：

  Two higher analogues of Lu-pinene, 2-isobutyl- and 2-isopropylapopinenes, promising chiral auxiliaries for asymmetric hydroboration, were readily synthesized from alpha-pinene in good chemical yield. A quantitative study was made of the rates and stoichiometry of the hydroboration of a number of representative 2-organylapopinenes (2-R-apopinenes) with representative boranes, such as BH3.SMe(2) (BMS) and BH3.THF, in order to develop a convenient procedure for the synthesis of mono- and bis(2-organylapoisopinocampheyl)boranes [2-R-apoisopinylborane (RapBH(2)) and bis(2-R-apoisopinyl)borane (Rap(2)BH), respectively],under investigation as possible improved asymmetric hydroborating reagents. It was evident that the sterically bulkier 2-R-apopinenes such as 2-phenyl- and 2-isopropylapopinenes reacted with boranes at room temperature to form essentially RapBH(2) in greater than or equal to 195 % yield, while a yield of greater than or equal to 90 % was realized in the case of 2-isobutylapopinene; However, alpha-pinene, and 2-ethyl- and 2-n-propylapopinenes smoothly reacted with boranes to form a mixture of RapBH(2) and Rap(2)BH. Under the reaction conditions employed, 2-ethyl-, 2-n-propyl-, 2-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes failed to produce clean Rap(2)BH. The rate of hydroboration decreased significantly with increase in bulk of the organyl group at the 2-position of the apopinene.

  DOI：

  10.1021/jo00087a016

文献信息

• 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
• Hydroboration. 94. Rates of Hydroboration of 2-Organylapopinenes with 9-Borabicyclo[3.3.1]nonane, Providing <i>B</i>-(2-Organylapoisopinocampheyl)-9-borabicyclo[3.3.1]nonanes, Potentially Valuable for the Asymmetric Reduction of Prochiral Ketones
  作者：Ulhas P. Dhokte、Herbert C. Brown

  DOI：10.1021/jo9617169

  日期：1997.2.1

  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.
• Hydroboration. 90. Synthesis of 2-Isobutyl- and 2-Isopropylapopinenes. Rates and Stoichiometry of the Hydroboration of 2-Organylapopinenes with Borane-Methyl Sulfide and Borane-Tetrahydrofuran
  作者：Herbert C. Brown、Ulhas P. Dhokte

  DOI：10.1021/jo00087a016

  日期：1994.4

  Two higher analogues of Lu-pinene, 2-isobutyl- and 2-isopropylapopinenes, promising chiral auxiliaries for asymmetric hydroboration, were readily synthesized from alpha-pinene in good chemical yield. A quantitative study was made of the rates and stoichiometry of the hydroboration of a number of representative 2-organylapopinenes (2-R-apopinenes) with representative boranes, such as BH3.SMe(2) (BMS) and BH3.THF, in order to develop a convenient procedure for the synthesis of mono- and bis(2-organylapoisopinocampheyl)boranes [2-R-apoisopinylborane (RapBH(2)) and bis(2-R-apoisopinyl)borane (Rap(2)BH), respectively],under investigation as possible improved asymmetric hydroborating reagents. It was evident that the sterically bulkier 2-R-apopinenes such as 2-phenyl- and 2-isopropylapopinenes reacted with boranes at room temperature to form essentially RapBH(2) in greater than or equal to 195 % yield, while a yield of greater than or equal to 90 % was realized in the case of 2-isobutylapopinene; However, alpha-pinene, and 2-ethyl- and 2-n-propylapopinenes smoothly reacted with boranes to form a mixture of RapBH(2) and Rap(2)BH. Under the reaction conditions employed, 2-ethyl-, 2-n-propyl-, 2-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes failed to produce clean Rap(2)BH. The rate of hydroboration decreased significantly with increase in bulk of the organyl group at the 2-position of the apopinene.