Dactyloxene-C

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: Dactyloxene-C
• 英文别名: (2S,5S,9S,10R)-2-ethenyl-2,6,9,10-tetramethyl-1-oxaspiro[4.5]dec-6-ene
• 化学式: C₁₅H₂₄O
• 分子量: 220.355
• InChiKey: CVZXLAAMZXBCMM-ZGKBOVNRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (5R)-Tetrahydro-5-methyl-5-vinyl-2-furanol benzoate 在 cerium(III) chloride 、 copper bromide dimethyl sulfide complex 、 Dowex 50X₄-400 、 叔丁基锂 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， -78.0~180.0 ℃ 、2.67 kPa 条件下， 反应 60.0h， 生成 Dactyloxene-C
  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

文献信息

• Synthesis and Absolute Configuration of Naturally Occurring Dactyloxene-B and -C
  作者：Bruno Maurer、Arnold Hauser、G�nther Ohloff

  DOI：10.1002/hlca.19800630844

  日期：1980.12.10

  (+)-trans-2, 5, 6-trimethyl-l-cyclohexene-l-carbaldehyde (1) which is shown to have the (5S, 6R)-configuration by chemical correlation with (+)-(2R, 3S, 6S)-2, 3, 6-trimethylcyclohexanone. The absolute configurations are therefore (2R, 5R, 9S, 10R) for (+)-dactyloxene-B and (2R, 5S, 9S, 10R) for (+)-dactyloxene-C.

  天然的（+） - dactyloxene-B （12）和-C （13）已经合成从（+）起始-反式-2，5-，6-三甲基-1-环己烯-1-甲醛（1） ，其被示出为通过与（+）-（2 R，3 S，6 S）-2,3,6-三甲基环己酮的化学相关具有（5 S，6 R）-构型。因此，对于（+）-己二烯-X-B，绝对构型为（2 R，5 R，9 S，10 R），对于（+）-二烯基-氧烯-C为（2 R，5 S，9 S，10 R）。
• Synthesis and Configuration of the Eight Diastereoisomeric Racemates of Dactyloxene-B. The relative configuration of dactyloxene-B and -C
  作者：Bruno Maurer、Arnold Hauser、Walter Thommen、Karl H. Schulte-Elte、G�nther Ohloff

  DOI：10.1002/hlca.19800630130

  日期：1980.1.23

  The eight possible diastereoisomeric racemates of dactyloxene-B have been synthesized by a non-stereoselective route and their configurations and predominant conformations determined by 360-MHz-1H-NMR. and 90.5-MHz-13C-NMR. spectroscopy. Natural dactyloxene-B and -C are shown to have the relative configuration rel-(2R, 5R, 9S, 10R) and rel-(2R, 5S, 9S, 10R), respectively.

  dactyloxene-B的八种可能的非对映异构外消旋体已通过非立体选择性途径合成，其构型和主要构象由360-MHz- 1 H-NMR确定。和90.5-MHz- 13 C-NMR。光谱学。天然dactyloxene-B和-C中示出为具有相对构型的rel - （2 - [R，5 - [R 9小号，10 - [R ）和相对- （2 - [R，5小号，9小号，10 - [R ）表示。
• 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.