(-)-2-isobutylapoisopinocampheol | 156327-02-5

• 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-isobutylapoisopinocampheol
• 英文别名: (1R,2R,3R,5S)-6,6-dimethyl-2-(2-methylpropyl)bicyclo[3.1.1]heptan-3-ol
• CAS: 156327-02-5
• 化学式: C₁₃H₂₄O
• 分子量: 196.333
• InChiKey: PKVYUBNJUYOFHH-IRCOFANPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N,O-bis(trimethylsilyl) acetamide 、 (-)-2-isobutylapoisopinocampheol 在 吡啶 作用下， 以 四氢呋喃 为溶剂， 生成
  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：

  (1S,5S)-6,6-dimethyl-2-(2-methylpropyl)bicyclo[3.1.1]hept-2-ene 生成 (-)-2-isobutylapoisopinocampheol
  参考文献：
  名称：

  Brown Herbert C., Dhokte Ulhas P., J. Org. Chem., 59 (1994) N 9, S 2365- 2369

  摘要：

  DOI：

文献信息

• Hydroboration. 91. Improved Procedure for the Synthesis of Optically Pure Bis-adducts,N,N,N,'N'-Tetramethylethylenediamine.cntdot.2-organylapoisopinocampheylboranes, from the Corresponding 2-Organylapopinenes of Lower Optical Purity. Conversion of These Adducts into 2-Organylapoisopinocampheylboranes, Useful Asymmetric Hydroborating Reagents
  作者：Herbert C. Brown、Ulhas P. Dhokte

  DOI：10.1021/jo00088a016

  日期：1994.5

  The higher analogues of alpha-pinene, such as 2-ethyl-, 2-n-propyl-, 8-isobutyl-, 2-phenyl-, and 2-isopropylapopinenes, were treated with borane-methyl sulfide (BMS) in the stoichiometry of 1.2:1, respectively, in anhydrous tetrahydrofuran (THF) at 25 degrees C, obtaining an equilibrium mixture of 2-organylapoisopinocampheylboranes (2-R-apoisopinylborane, RapBH(2)) as major and bis(2-organylapoisopinocampheyl)borane [bis(2-R-apoisopinyl)borane, Rap(2)BH] as minor constituents. Treatment of the equilibrium mixture of boranes with tetramethylethylenediamine (TMEDA) at 34 degrees C readily and selectively provided the optically pure bis(2-organylapoisopinocampheylborane) T adducts, (RapBH(2))(2).TMEDA, in satisfactory yield. This reaction is quite general and appears to be broadly applicable to the conversion of the sterically bulkier 2-organylapopinenes (2-R-apopinenes) with widely varied steric requirements and lower optical purity (87-92% ee) into the corresponding optically pure (RapBH(2))(2).TMEDA derivatives, approaching greater than or equal to 99% ee. Treatment of the crystalline bis-adduct in ethyl ether with BF3.EE precipitates (BF3)(2).TMEDA and provides RapBH(2) of essentially greater than or equal to 99% ee, enantiomerically purer than the 2-R-apopinenes of 87-92% ee utilized for these preparations.