2-(2-Propenyl)cyclooctanone | 38931-77-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(2-Propenyl)cyclooctanone
• 英文别名: 2-allylcyclooctanone；2-Allylcyclooctan-1-on；2-Allyl-cyclooctanon；2-Allylcyclooctanon；2-(Prop-2-en-1-yl)cyclooctan-1-one；2-prop-2-enylcyclooctan-1-one
• CAS: 38931-77-0
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: QWMSGRAERMWGNJ-UHFFFAOYSA-N

物化性质

• 沸点：
  101-102 °C(Press: 10 Torr)
• 密度：
  0.886±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  2-(2-Propenyl)cyclooctanone 在 过氧化氢苯甲酰 、 氢溴酸 、 碳酸氢钠 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 正戊烷 为溶剂， 反应 3.0h， 生成 trans-8,9-epoxybicyclo<6.3.0>undecane
  参考文献：
  名称：

  Intramolecular sulfur ylide additions to ketones

  摘要：

  DOI：

  10.1021/jo00148a025
• 作为产物：
  描述：

  2-氧-1-环辛烷羧酸 在 氢氧化钾 、 sodium ethanolate 作用下， 以 乙醇 为溶剂， 生成 2-(2-Propenyl)cyclooctanone
  参考文献：
  名称：

  Saharia,G.S.; Tyagi,M.P., Journal of the Indian Chemical Society, 1972, vol. 49, p. 611 - 613

  摘要：

  DOI：

文献信息

• Mn(III)-Based Oxidative Free-Radical Cyclizations of Unsaturated Ketones
  作者：Bridget McCarthy Cole、Luning Han、Barry B. Snider

  DOI：10.1021/jo961199u

  日期：1996.1.1

  free-radical cyclization of unsaturated ketones is a versatile synthetic procedure with broad applicability. For example, oxidation of cyclopentanone 1a with 2 equiv of Mn(OAc)(3).2H(2)O and 1 equiv of Cu(OAc)(2).H(2)O in AcOH at 80 degrees C for 1.5 h affords 75% of bicyclo[3.2.1]oct-3-en-8-one 8a and 15% of bicyclo[3.2.1]oct-2-en-8-one 9a. Bridged bicyclic ketones that cannot enolize further are isolated

  Mn（III）基的不饱和酮的氧化自由基环化是一种通用的合成方法，具有广泛的适用性。例如，在80摄氏度的条件下，在AcOH中用2当量的Mn（OAc）（3）.2H（2）O和1当量的Cu（OAc）（2）.H（2）O氧化环戊酮1a 1.5小时得到75％的双环[3.2.1] oct-3-en-8-one 8a和15％的双环[3.2.1] oct-2-en-8-one 9a。分离出不能进一步烯醇化的桥联双环酮，收率很高。可以烯化的单环β，γ-不饱和酮被进一步氧化，得到γ-乙酰氧基烯酮。从2-烯丙基环己酮（56a）以52％的收率形成双环[3.3.1] non-2-en-9-one（57a）表明，动力学控制的烯醇化是α-酮自由基形成过程中的决定速率的步骤。各种各样的示例描述了范围，限制，
• A Novel Pentannulation Sequence. Facile Access to Key Intermediates for the Synthesis of<i>Exaltone</i>® and Muscone
  作者：Charles Fehr

  DOI：10.1002/hlca.19830660817

  日期：1983.12.14

  Treatment of the sulfonyl ketones 1a and 1b with potassium t-butoxide in toluene or with potassium hydroxide in toluene/dimethyl sulfoxide affords in high yield the bicyclic dienes 3a and 3b, important precursors for Exaltone® and (±)-muscone. An application of this novel pentannulation sequence is demonstrated for the sulfonyl ketones 6, 10, and 14. An intermolecular variant is exemplified by the

  用甲苯中的叔丁醇钾或甲苯/二甲基亚砜中的氢氧化钾处理磺酰基酮1a和1b，可高产率获得双环二烯3a和3b，这是Exaltone®和（±）-麝香酮的重要前体。该新的戊烯醛化序列的应用已证明可用于磺酰基酮6、10和14。分子间的变体以二烯22的合成为例。
• Carbocyclic Amino Ketones by Bredt's Rule‐Arrested Kulinkovich–de Meijere Reaction
  作者：Paul B. Finn、Brenden P. Derstine、Scott McN. Sieburth

  DOI：10.1002/anie.201509983

  日期：2016.2.12

  reaction, involves two carbon–carbon bond‐forming steps. Strategic use of a tricyclic intermediate can arrest the process if the second step requires formation of a bridgehead double bond. Use of this Bredt's rule constraint results in the production of carbocyclic amino ketones, key alkaloid building blocks.

  Ti II介导的由烯烃和酰胺形成的环丙胺，Kulinkovich-de Meijere反应涉及两个碳-碳键形成步骤。如果第二步需要形成桥头双键，则三环中间体的战略性使用可中止该过程。使用此Bredt规则约束会产生碳环氨基酮（关键生物碱构件）的产生。
• Synthesis of Oxa-Bridged Medium-Sized Carbocyclic Rings via Prins Cyclization
  作者：Min-Shou Wang、Zheng Wang、Wen Chen、Xiaodong Yang、Hongbin Zhang

  DOI：10.1021/acs.orglett.9b00491

  日期：2019.3.15

  of oxa-bridged carbocyclic units based on intramolecular Prins reaction of dioxinones. Our new synthetic approach is flexible and practical and has been successfully applied to the preparation of highly functionalized seven-, eight-, and nine-membered carbocycles. The potential utility of this approach has also been demonstrated in a model study toward construction of the 7,8-fused ring system presented

  在本文中，我们报告了一种基于二恶英酮分子内Prins反应合成氧杂桥联碳环单元的新方法。我们的新合成方法灵活实用，已成功应用于制备高度功能化的七元，八元和九元碳素自行车。这种方法的潜在效用也已在新阿比索霉素D中提出的构建7,8-稠合环系统的模型研究中得到了证明。
• Revisiting [3 + 3] Route to 1,3-Cyclohexanedione Frameworks:  Hidden Aspect of Thermodynamically Controlled Enolates
  作者：Teruhiko Ishikawa、Ryuichiro Kadoya、Masaki Arai、Haruka Takahashi、Yumi Kaisi、Tomohiro Mizuta、Kazusa Yoshikai、Seiki Saito

  DOI：10.1021/jo010325d

  日期：2001.11.1

  We have revisited the traditional consecutive Michael-Claisen [3 + 3] process (MC-[3 + 3]) promising the synthesis of a cyclohexane-1,3-dione derivatives from nonactivated simple ketones and enoates and evaluated its potential in modern organic synthesis. Twenty to thirty examples were demonstrated to be effective. The reactions exhibited remarkable regioselectivity with the Michael addition proceeding through nucleophilic attack by the more hindered site of the ketones without exception. The subsequent Claisen condensation resulted in the formation of carbon-carbon bonds between less hindered site of the ketones and acyl carbon of the enoates. The MC-[3 + 3] process described is useful for the synthesis of Taxol A-ring synthons in multigram quantities and for the synthesis of other six-membered carbocyclic compounds. A number of control experiments have been conducted to provide strong support for the mechanism of this MC-[3 + 3].