rac-(Z)-3-(4a,8-dimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)but-2-en-1-ol | 302902-94-9

• 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: rac-(Z)-3-(4a,8-dimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)but-2-en-1-ol
• 英文别名: (Z)-3-(4a,8-dimethyl-4,5,6,7-tetrahydro-3H-naphthalen-2-yl)but-2-en-1-ol
• CAS: 302902-94-9
• 化学式: C₁₆H₂₄O
• 分子量: 232.366
• InChiKey: NQTFRVCTCQQBPV-GHXNOFRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  rac-(Z)-3-(4a,8-dimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)but-2-en-1-ol 在 碘 、 戴斯-马丁氧化剂 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 4.08h， 生成 (2E)-3-(3,4,4a,5,6,7-hexahydro-4a,8-dimethyl-2-naphthalenyl)-3-methyl-2-propenal
  参考文献：
  名称：

  Stereocontrolled Synthesis of 6-s-cis- and 6-s-trans-Locked 9Z-Retinoids by Hydroxyl-Accelerated Stille Coupling of (Z)-Tri-n-Butylstannylbut-2-en-1-ol and Bicyclic Dienyl Triflates

  摘要：

  Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5 and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.

  DOI：

  10.1021/jo9917588
• 作为产物：
  描述：

  4,4a,5,6,7,8-六氢-4a,8-二甲基萘-2(3H)-酮 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 2,6-二叔丁基-4-甲基吡啶 、 三苯胂 作用下， 以 N-甲基吡咯烷酮 、 二氯甲烷 为溶剂， 反应 13.5h， 生成 rac-(Z)-3-(4a,8-dimethyl-3,4,4a,5,6,7-hexahydronaphthalen-2-yl)but-2-en-1-ol
  参考文献：
  名称：

  Stereocontrolled Synthesis of 6-s-cis- and 6-s-trans-Locked 9Z-Retinoids by Hydroxyl-Accelerated Stille Coupling of (Z)-Tri-n-Butylstannylbut-2-en-1-ol and Bicyclic Dienyl Triflates

  摘要：

  Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5 and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.

  DOI：

  10.1021/jo9917588

文献信息

• Stereocontrolled Synthesis of 6-<i>s</i>-<i>cis</i>- and 6-<i>s</i>-<i>trans</i>-Locked 9<i>Z</i>-Retinoids by Hydroxyl-Accelerated Stille Coupling of (<i>Z</i>)-Tri-<i>n</i>-Butylstannylbut-2-en-1-ol and Bicyclic Dienyl Triflates
  作者：Beatriz Domínguez、Yolanda Pazos、Angel R. de Lera

  DOI：10.1021/jo9917588

  日期：2000.9.1

  Analogues of 9-cis-retinoic acid with locked 6-s-cis and 6-s-trans conformations have been stereoselectively synthesized using a Stille coupling reaction between bicyclic dienyl triflates (5 and 6, respectively) and (Z)-tributylstannylbut-2-en-1-ol (7) to stablish the Z geometry of the polyenic side chain. The mild conditions (25 degrees C, 30 min) of this coupling stand in contrast to the reluctance of the isomeric (E)-tributylstannylbut-2-en-1-ol (18) to react with triflates 5/6. The significant rate differences experimentally observed in Stille reactions between isomeric (Z)- and (E)-tri-n-butylstannylalkenols in favor of the former isomer, even with highly hindered alkenyl triflates, is ascribed to internal coordination of palladium to the heteroatom in the presumably rate-limiting transmetalation step. Dienals and trienals with an E geometry, which are not efficiently available by direct coupling of the corresponding triflates and E-stannanes, can in turn be obtained by isomerization of their Z-isomers.