2-Phenylapopinene

• 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: 6,6-Dimethyl-2-phenylbicyclo[3.1.1]hept-2-ene
• 化学式: C₁₅H₁₈
• 分子量: 198.308
• InChiKey: SYRDENIJTJYALZ-UHFFFAOYSA-N

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 生成 (+)-2-phenylapoisopinocampheol
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jo00088a016

文献信息

• Hydroboration. 93. Convenient Conversion of Optically Pure 2-Organylapopinenes into the (2-Organylapoisopinyl)dihaloboranes Potentially Valuable for Asymmetric Synthesis via Chiral Organoboranes
  作者：Ulhas P. Dhokte、Herbert C. Brown

  DOI：10.1021/om960240g

  日期：1996.8.6

  Optically pure and sterically varied (2-organylapoisopinyl)dihaloboranes [RapBX2, R = Me (except for X = I), Et, Pr, i-Bu, Ph, i-Pr, X = Cl, Br, I], potentially important reagents for asymmetric synthesis, are conveniently prepared by the in situ reduction and hydroboration reaction of boron trihalide, trimethylsilane, and 2-organylapopinenes (2-R-apopinenes) under mild reaction conditions in essentially

  可能是光学纯且呈空间变化的（2-organylapoisopinyl）二卤环烷酮[RapBX 2，R = Me（X = I除外），Et，Pr，i -Bu，Ph，i -Pr，X = Cl，Br，I]，不对称合成的重要试剂可通过在温和的反应条件下原位还原三卤化硼硼，三甲基硅烷和2-有机基罂粟碱（2-R-罂粟碱）并进行硼氢化反应来制备，其定量产率基本可得。不幸的是，尽管更大体积的2-R-罂粟碱提供了所需的RapBI 2衍生物，但是不能通过该方法合成IpcBI 2（RapBI 2，R = Me）。
• 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.