[(2R,5R,9S,10R)-2-ethenyl-2,9,10-trimethyl-1-oxaspiro[4.5]dec-6-en-6-yl] trifluoromethanesulfonate | 152999-73-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: [(2R,5R,9S,10R)-2-ethenyl-2,9,10-trimethyl-1-oxaspiro[4.5]dec-6-en-6-yl] trifluoromethanesulfonate
• CAS: 152999-73-0
• 化学式: C₁₅H₂₁F₃O₄S
• 分子量: 354.391
• InChiKey: LVQCDKKDGKPDRH-UZGDPCLZSA-N

物化性质

• 沸点：
  373.9±42.0 °C(predicted)
• 密度：
  1.28±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  23
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  61
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(2R,5R,9S,10R)-2-ethenyl-2,9,10-trimethyl-1-oxaspiro[4.5]dec-6-en-6-yl] trifluoromethanesulfonate 在 copper bromide dimethyl sulfide complex 、 甲基锂 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以41%的产率得到(2R,5S,6R,7S)-2-ethenyl-2,6,7-trimethyl-1-oxaspiro[4.5]dec-9-ene
  参考文献：
  名称：

  Oxonium ion-initiated pinacolic ring expansion reactions. Application to the enantioselective synthesis of the spirocyclic sesquiterpene ethers dactyloxene-B and -C

  摘要：

  A convergent synthesis of dactyloxene-B (1) and -C (2) from a common optically active intermediate in seven steps has been achieved. Ozonolysis of(R)-(-)-linalool proceeded regioselectively to deliver a lactol, the benzoate of which when thermolyzed gave dihydrofuran 7. The second building block, levorotatory cyclopentanone 8, was produced by kinetically controlled lipase-induced hydrolysis of chloroacetate 15b. Saponification and oxidation of the less reactive ester was sufficient to provide (-)-8 whose condensation with the cerate of 7 gave rise to 19 and set the stage for implementation of the key structural rearrangement step. When stirred with Dowex resin, 19 was isomerized to four ketones. Following chromatographic separation, 20 and 21 were independently transformed into the target molecules via a two-step sequence. The spectral and optical properties of the two dactyloxenes compared very favorably with those reported earlier.

  DOI：

  10.1021/jo00106a033
• 作为产物：
  描述：

  (R)-芳樟醇 在 cerium(III) chloride 、 Dowex 50x4-400 resin 、 叔丁基锂 、 双(三甲基硅烷基)氨基钾 、 臭氧 、 三乙胺 作用下， 以 吡啶 、 二氯甲烷 为溶剂， -78.0~180.0 ℃ 、2.67 kPa 条件下， 生成 [(2R,5R,9S,10R)-2-ethenyl-2,9,10-trimethyl-1-oxaspiro[4.5]dec-6-en-6-yl] trifluoromethanesulfonate
  参考文献：
  名称：

  Enantioselective synthesis of natural (+)-dactyloxene-B and -C by actuation of oxonium ion-initiated pinacol rearrangement

  摘要：

  A direct route is described for assembling the spirocyclic framework of two sesquiterpene ethers derived biogenetically from the cyclization of farnesol with rearrangement of a methyl group.

  DOI：

  10.1016/s0040-4039(00)73835-4

文献信息

• Oxonium ion-initiated pinacolic ring expansion reactions. Application to the enantioselective synthesis of the spirocyclic sesquiterpene ethers dactyloxene-B and -C
  作者：Marc D. Lord、Joanna T. Negri、Leo A. Paquette

  DOI：10.1021/jo00106a033

  日期：1995.1

  A convergent synthesis of dactyloxene-B (1) and -C (2) from a common optically active intermediate in seven steps has been achieved. Ozonolysis of(R)-(-)-linalool proceeded regioselectively to deliver a lactol, the benzoate of which when thermolyzed gave dihydrofuran 7. The second building block, levorotatory cyclopentanone 8, was produced by kinetically controlled lipase-induced hydrolysis of chloroacetate 15b. Saponification and oxidation of the less reactive ester was sufficient to provide (-)-8 whose condensation with the cerate of 7 gave rise to 19 and set the stage for implementation of the key structural rearrangement step. When stirred with Dowex resin, 19 was isomerized to four ketones. Following chromatographic separation, 20 and 21 were independently transformed into the target molecules via a two-step sequence. The spectral and optical properties of the two dactyloxenes compared very favorably with those reported earlier.
• Enantioselective synthesis of natural (+)-dactyloxene-B and -C by actuation of oxonium ion-initiated pinacol rearrangement
  作者：Leo A. Paquette、Marc D. Lord、Joanna T. Negri

  DOI：10.1016/s0040-4039(00)73835-4

  日期：1993.9

  A direct route is described for assembling the spirocyclic framework of two sesquiterpene ethers derived biogenetically from the cyclization of farnesol with rearrangement of a methyl group.