3,4,7,7-tetramethylbicyclo<3.3.0>oct-3-en-2-one | 123675-66-1

• 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: 3,4,7,7-tetramethylbicyclo<3.3.0>oct-3-en-2-one
• 英文别名: (3aR,6aS)-2,3,5,5-tetramethyl-3a,4,6,6a-tetrahydropentalen-1-one
• CAS: 123675-66-1
• 化学式: C₁₂H₁₈O
• 分子量: 178.274
• InChiKey: BKUUBQXZRFAZME-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,4,7,7-tetramethylbicyclo<3.3.0>oct-3-en-2-one 在 sodium chlorite 、 sodium dihydrogenphosphate 、 selenium(IV) oxide 作用下， 以 叔丁醇 为溶剂， 反应 7.5h， 生成 4-carboxy-3,7,7-trimethylbicyclo<3.3.0>oct-3-en-2-one
  参考文献：
  名称：

  Synthesis of (.+-.)-marasmic acid via 1-oxaspirohexane rearrangement

  摘要：

  DOI：

  10.1021/ja00158a042
• 作为产物：
  描述：

  methyl 2-hydroxy-5,5-dimethylcyclohex-1-enecarboxylate 在 六甲基磷酰三胺 、 溴 、 叔丁基锂 、 对甲苯磺酸 、 乙二醇 、 三乙胺 作用下， 以 四氢呋喃 、 四氯化碳 、 乙醚 、 氯仿 、 苯 为溶剂， 反应 122.0h， 生成 3,4,7,7-tetramethylbicyclo<3.3.0>oct-3-en-2-one
  参考文献：
  名称：

  An ynolate-initiated tandem process giving cyclopentenones: total synthesis of cucumin E

  摘要：

  A total synthesis of cucumin E, a novel type of triquinane natural product, has been accomplished. The strategy is based on an ynolate-initiated tandem [2+2] cycloaddition-Dieckmann condensation, followed by decarboxylation, giving cyclopentenones. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(02)01015-8

文献信息

• Synthesis of the sesquiterpene (±)-ceratopicanol: Use of radicals derived from epoxides
  作者：Derrick L.J. Clive、Steven R. Magnuson

  DOI：10.1016/0040-4039(94)02158-8

  日期：1995.1

  The sesquiterpene (±)-ceratopicanol [(±)-1] was synthesized by a route based on Claisen rearrangement (7 → 8) and radical cyclization (16α, 16β → 17α, 17β). Certain limitations on vinyl radical cyclization were observed, and so the required radical was generated by titanium-induced opening of an epoxide.

  倍半萜烯（±）-ceratopicanol [（±）-1]是基于Claisen重排（一路线合成7 → 8）和自由基环化（16 α，16 β→ 17 α，17 β）。观察到乙烯基自由基环化的某些限制，因此所需的自由基是由钛诱导的环氧化物的打开生成的。
• Cyclopentannulation by an Iterative Process of Sequential Claisen Rearrangement and Enyne Radical Closure:  Routes to Triquinane and Propellane Systems and Use in the Synthesis of (±)-Ceratopicanol
  作者：D. L. J. Clive、Steven R. Magnuson、Hartford W. Manning、Darrin L. Mayhew

  DOI：10.1021/jo951930h

  日期：1996.1.1

  Cycloalkenyl acetylenes 4, which are easily prepared from allylic alcohols by Claisen rearrangement and homologation (1 --> 4), generally undergo radical cyclization (4 --> 6) on treatment with stannyl radicals. The products (6) can themselves be converted into allylic alcohols, so that the annulation sequence can then be repeated. In certain cases enyne cyclization initiated by stannyl radicals does not work, but an alternative process (cf. Scheme 9) of epoxide opening with bis(cyclopentadienyl)titanium(III) chloride can then be used. Di- and triquinanes (Scheme 3) were made by the stannyl radical approach; the epoxide route was used to prepare a simple propellane (Scheme 4) and in a synthesis of (+)-ceratopicanol (Schemes 5 and 9).
• TOBE, YOSHITO;YAMASHITA, DAI;TAKAHASHI, TOHRU;INATA, MASASHI;SATO, JUN-IC+, J. AMER. CHEM. SOC., 112,(1990) N, C. 775-779
  作者：TOBE, YOSHITO、YAMASHITA, DAI、TAKAHASHI, TOHRU、INATA, MASASHI、SATO, JUN-IC+

  DOI：——

  日期：——
• An ynolate-initiated tandem process giving cyclopentenones: total synthesis of cucumin E
  作者：Mitsuru Shindo、Yusuke Sato、Kozo Shishido

  DOI：10.1016/s0040-4039(02)01015-8

  日期：2002.7

  A total synthesis of cucumin E, a novel type of triquinane natural product, has been accomplished. The strategy is based on an ynolate-initiated tandem [2+2] cycloaddition-Dieckmann condensation, followed by decarboxylation, giving cyclopentenones. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of (.+-.)-marasmic acid via 1-oxaspirohexane rearrangement
  作者：Yoshito Tobe、Dai Yamashita、Tohru Takahashi、Masashi Inata、Junichi Sato、Kiyomi Kakiuchi、Kazuya Kobiro、Yoshinobu Odaira

  DOI：10.1021/ja00158a042

  日期：1990.1