3-methylenetricyclo<6.3.0.0^1,4>undecan-5-one | 138124-75-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-methylenetricyclo<6.3.0.0^1,4>undecan-5-one
• 英文别名: 3-methylenetricyclo[6.3.0.0^1,4]undecan-5-one；(1R,4R,8S)-3-methylidenetricyclo[6.3.0.01,4]undecan-5-one
• CAS: 138124-75-1
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: KGMWAMPGXROWNW-ZMLRMANQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• 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-methylenetricyclo<6.3.0.0^1,4>undecan-5-one 在 samarium diiodide 、 lithium chloride 、 叔丁醇 作用下， 以 四氢呋喃 为溶剂， 反应 0.01h， 以98%的产率得到
  参考文献：
  名称：

  Sm（II）诱导的1,2-重排反应与亚甲基双环[4.2.0]辛酮扩环合成亚甲基双环[3.2.1]辛醇

  摘要：

  描述了由Sm（II）诱导的1，2-重排与亚甲基环丁烷的扩环，将亚甲基双环[4.2.0]辛酮直接转化为亚甲基双环[3.2.1]辛醇。优化了三个条件，以使该方法适用于各种基材。提出了一种重排机制，涉及通过酮基-烯烃环化生成酮基自由基和环戊烷化，然后进行自由基裂解和随后的质子化。

  DOI：

  10.1021/acs.orglett.7b01604
• 作为产物：
  描述：

  丙二烯 、 1,2,3,6,7,7a-hexahydro-5H-inden-5-one 以 二氯甲烷 为溶剂， 反应 5.0h， 以81%的产率得到3-methylenetricyclo<6.3.0.0^1,4>undecan-5-one
  参考文献：
  名称：

  Sm（II）诱导的1,2-重排反应与亚甲基双环[4.2.0]辛酮扩环合成亚甲基双环[3.2.1]辛醇

  摘要：

  描述了由Sm（II）诱导的1，2-重排与亚甲基环丁烷的扩环，将亚甲基双环[4.2.0]辛酮直接转化为亚甲基双环[3.2.1]辛醇。优化了三个条件，以使该方法适用于各种基材。提出了一种重排机制，涉及通过酮基-烯烃环化生成酮基自由基和环戊烷化，然后进行自由基裂解和随后的质子化。

  DOI：

  10.1021/acs.orglett.7b01604

文献信息

• Acid-Catalyzed Rearrangement of an Allene-Cyclohexenone Photoadduct and its Application in the Synthesis of (±)-Pentalenene
  作者：Kiyomi Kakiuchi、Tsumoru Morimoto、Tomoyuki Horiguchi、Kuriko Yamada、Ken Tsutsumi、Hideo Kurosawa

  DOI：10.1055/s-2004-815988

  日期：——

  The acid-catalyzed rearrangement of 3-methylenetricyclo[6.3.0.0 1 . 4 ]undecan-5-one (5), prepared via the photocycloaddition of cyclohexenone to allene, gave the triquinanes. In addition, the method was applied to the synthesis of (′)-pentalenene.

  3-亚甲基三环的酸催化重排[6.3.0.0 1 . 通过环己烯酮与丙二烯的光环加成反应制备的 4 ]undecan-5-one (5) 得到三醌。此外，该方法还应用于(')-戊二烯的合成。
• Skeletal Rearrangement of 8-Methylenebicyclo[4.2.0]octan-2-ones with Mercury(II) Perchlorate
  作者：Kiyomi Kakiuchi、Tomoyuki Horiguchi、Koichi Minato、Yoshito Tobe、Hideo Kurosawa

  DOI：10.1021/jo00125a048

  日期：1995.10

  Skeletal rearrangement of C6-substituted 8-methylenebicyclo[4.2.0]octan-2-ones 1a-d and 16 with mercury(II) perchlorate was examined, and the remarkable substituent effect on the rearrangement was elucidated. Reactions of the ketones la and Ib having methyl and ethyl groups with Hg(ClO4)(2) . 3H(2)O gave the bicyclo[2.2.2]octanones 2a,b and 3a,b along with a small amount of the bicyclo[3.3.1]nonanones 4a,b, respectively. The yield of the bicyclo[3.3.1] ketone 4c increased in the reaction of the isopropyl derivative Ic. The tert-butyl derivative Id afforded the bicyclo[3.3.1]nonanone 4d as a major product together with a mixture of the bicyclo[2.2.2]octanones 2d and 3d. The remarkable substituent effect is explained based on the stability of the conformers 7 and 10 of the postulated intermediate 6. The intermediacy of 6 was verified by reaction of 6b prepared independently under similar conditions. Similar treatment of the tricyclic ketone 16 yielded the bicyclo[3.3.1]nonanone 19 as a major product along with a small amount of the bicyclo[2.2.2] ketones 17 and 18. The structures of products were determined by NMR spectral data including 2D C-13-INADEQUATE spectrum of 19 and the X-ray crystallographic analysis of 4d. (+/-)-Desdimethyldihydroclovene (22) was easily synthesized from 19 via radical deoxygenation followed by transformation of the tertiary hydroxyl group to the methyl group.
• Construction of the bicyclo[6.3.0]undecane skeleton via ring opening of tricyclo[6.3.0.01,4]undecan-5-ones
  作者：Kiyomi Kakiuchi、Keisuke Fukunaga、Mamoru Jimbo、Bunji Yamaguchi、Yoshito Tobe

  DOI：10.1021/jo00029a047

  日期：1992.1
• Synthesis of Methylenebicyclo[3.2.1]octanol by a Sm(II)-Induced 1,2-Rearrangement Reaction with Ring Expansion of Methylenebicyclo[4.2.0]octanone
  作者：Kazuhiko Takatori、Shoya Ota、Kenta Tendo、Kazuma Matsunaga、Kokoro Nagasawa、Shinya Watanabe、Atsushi Kishida、Hiroshi Kogen、Hiroto Nagaoka

  DOI：10.1021/acs.orglett.7b01604

  日期：2017.7.21

  Direct conversion of methylenebicyclo[4.2.0]octanone to methylenebicyclo[3.2.1]octanol by a Sm(II)-induced 1,2-rearrangement with ring expansion of the methylenecyclobutane is described. Three conditions were optimized to allow the adaptation of this approach to various substrates. A rearrangement mechanism is proposed involving the generation of a ketyl radical and cyclopentanation by ketyl–olefin

  描述了由Sm（II）诱导的1，2-重排与亚甲基环丁烷的扩环，将亚甲基双环[4.2.0]辛酮直接转化为亚甲基双环[3.2.1]辛醇。优化了三个条件，以使该方法适用于各种基材。提出了一种重排机制，涉及通过酮基-烯烃环化生成酮基自由基和环戊烷化，然后进行自由基裂解和随后的质子化。