cis-2,3-Dimethyl-2-(3-oxobutyl)cyclohexanone | 184653-52-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-2,3-Dimethyl-2-(3-oxobutyl)cyclohexanone
• 英文别名: (2S,3R)-2,3-dimethyl-2-(3-oxobutyl)cyclohexan-1-one
• CAS: 184653-52-9
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: GJBDAYUXOLDJRA-SKDRFNHKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  cis-2,3-Dimethyl-2-(3-oxobutyl)cyclohexanone 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以74%的产率得到(rel-4aS,5R)-4a,5-dimethyl-4,4a5,6,7,8-hexahydronaphthalen-2(3H)-one
  参考文献：
  名称：

  五种天然艾草双倍型倍半萜的全合成†

  摘要：

  通过一个普通的合成中间体，在4至12个步骤中完成了5种天然艾草双酚倍半萜类化合物的第一个总合成。合成具有双迈克尔加成反应，罗宾逊环化，不饱和酮的α-烯丙基化和Pd催化的Suzuki偶联反应以安装侧链。这种合成策略可以很容易地扩展到其他具有类似双环骨架的天青石型倍半萜。

  DOI：

  10.1039/c7ob02769a
• 作为产物：
  描述：

  2-甲基-2-环己烯-1-酮 在 palladium on activated charcoal 甲基碘化镁 、 氢气 、 copper(l) cyanide 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、506.62 kPa 条件下， 反应 72.42h， 生成 cis-2,3-Dimethyl-2-(3-oxobutyl)cyclohexanone
  参考文献：
  名称：

  Efficient Trapping of Ketone Enolates With Acrylate and β-Sulfonylacrylate Thioesters, β-Sulfonyl-, β-Sulfinyl- and β-Chloro-Vinyl Ketones; Facile Preparation of a Hydrindanone, cis-Dimethyloctalone, and Unsaturated 1,5-Dicarbonyl Compounds

  摘要：

  串联共轭加成-环闭合反应涉及将锂化的(E)-2-丁烯基二苯氧化膦与 2-甲基-2-环戊烯酮共轭加成而生成的烯酸锂与两摩尔的硫代丙烯酸叔丁酯反应，生成氢茚醇，并在铜(I)存在下生成氢茚醇衍生的内酯。β-磺酰基丙烯酸酯苯基和 t-丁基硫代酯、β-氯乙烯基、β-磺酰基和 β-磺酰基乙烯基酮与上述烯醇发生反应，并与 2-甲基环己烯酮与甲基缩二脲共轭加成生成的烯醇发生反应，生成不饱和的 1,5-二羰基化合物。其中，β-氯乙烯酮的反应速度快，产率高。2-Methylcyclohexenone 由此转化为顺式二甲基辛酮；这一转化说明了 β-氯乙烯基甲基酮在罗宾逊环化反应中的有效性。此外，还记录了 2,6-二甲基环己酮的锂烯醇和钛烯醇与 β-取代烯酮的反应，从而得到相应的不饱和 1,5-二羰基化合物和其他产物。

  DOI：

  10.1071/ch9901375

文献信息

• A practical and efficient preparation of (−)-(4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone: a key intermediate in the synthesis of (−)-dehydrofukinone
  作者：Rossana A. Schenato、Éverton M. dos Santos、Beatriz S.M. Tenius、Paulo R.R. Costa、Ignez Caracelli、Julio Zukerman-Schpector

  DOI：10.1016/s0957-4166(01)00089-1

  日期：2001.3

  A novel diastereoselective route to octalone (−)-1 has been developed. The key step involves an asymmetric Michael addition of the corresponding chiral secondary enamines derived from (S)-(−)-1-phenylethylamine and (3R)-2,3-dimethylcyclohexanone to methyl vinyl ketone. This enone was successfully transformed into the eremophilane-type sesquiterpenoid (−)-dehydrofukinone.

  已经开发了一种新颖的非对映选择性途径，可以生成八-（- 1）-1。关键步骤涉及将衍生自（S）-（-）-1-苯基乙胺和（3 R）-2,3-二甲基环己酮的相应手性仲烯胺不对称迈克尔加成到甲基乙烯基酮上。该烯酮已成功转化为全草苷型倍半萜类（-）-脱氢富马酮。
• Efficient Trapping of Ketone Enolates With Acrylate and β-Sulfonylacrylate Thioesters, β-Sulfonyl-, β-Sulfinyl- and β-Chloro-Vinyl Ketones; Facile Preparation of a Hydrindanone, cis-Dimethyloctalone, and Unsaturated 1,5-Dicarbonyl Compounds
  作者：RJ Dancer、RK Haynes、WA Loughlin、SC Vonwiller

  DOI：10.1071/ch9901375

  日期：——

  Tandem conjugate addition-ring closure involving reaction of the lithium enolate arising from conjugate addition of lithiated (E)-but-2- enyldiphenylphosphine oxide to 2-methyl-cyclopent-2-enone with two moles of t-butylthioacrylate generates a hydrindanol, and, in the presence of copper(I), a lactone derived from the hydrindanol. β-Sulfonylacrylate phenyl and t-butyl thioesters, β-chlorovinyl, β- sulfonyl- and β-sulfinyl-vinyl ketones react with the foregoing enolate, and with the enolate generated through conjugate addition of a methylcuprate to 2-methylcyclohexenone to give unsaturated 1,5-dicarbonyl compounds. The β-chlorovinyl ketones in particular react rapidly and in high yield. 2-Methylcyclohexenone has thereby been converted into a cis-dimethyl octalone; the conversion illustrates the effectiveness of β-chlorovinyl methyl ketone in the Robinson annelation. Reactions of the lithium enolate and titanium enol of 2,6- dimethylcyclohexanone with the β-substituted enones to give the corresponding unsaturated 1,5-dicarbonyl compounds and other products are also recorded.

  串联共轭加成-环闭合反应涉及将锂化的(E)-2-丁烯基二苯氧化膦与 2-甲基-2-环戊烯酮共轭加成而生成的烯酸锂与两摩尔的硫代丙烯酸叔丁酯反应，生成氢茚醇，并在铜(I)存在下生成氢茚醇衍生的内酯。β-磺酰基丙烯酸酯苯基和 t-丁基硫代酯、β-氯乙烯基、β-磺酰基和 β-磺酰基乙烯基酮与上述烯醇发生反应，并与 2-甲基环己烯酮与甲基缩二脲共轭加成生成的烯醇发生反应，生成不饱和的 1,5-二羰基化合物。其中，β-氯乙烯酮的反应速度快，产率高。2-Methylcyclohexenone 由此转化为顺式二甲基辛酮；这一转化说明了 β-氯乙烯基甲基酮在罗宾逊环化反应中的有效性。此外，还记录了 2,6-二甲基环己酮的锂烯醇和钛烯醇与 β-取代烯酮的反应，从而得到相应的不饱和 1,5-二羰基化合物和其他产物。
• First stereoselective synthesis of (4aS,5R)-4,4a,5,6,7,8-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone
  作者：Xavier Cuesta、Asensio González、Josep Bonjoch

  DOI：10.1016/s0957-4166(99)00349-3

  日期：1999.8

  The synthesis of enantiomerically pure (4aS,5R)-hexahydro-4a,5-dimethyl-2(3H)-naphthalenone (-)-1 is described for the first time. The synthesis starts from (R)-3-methylcyclohexanone and involves the preparation of piers enol lactone 6 in its enantiopure form as the key intermediate. Treatment of (+)-6 with methyl lithium followed by an intramolecular aldol reaction gives the bicyclic enone (-)-1. (C) 1999 Elsevier Science Ltd. All rights reserved.
• An efficient synthesis of the natural (+)-fulvanin 1
  作者：Philippe Dagneau、Perséphone Canonne

  DOI：10.1016/0957-4166(96)00370-9

  日期：1996.10

  Pulegone was used for the first total synthesis of (+)-fulvanin 1 adopting chiron approach. Pertinent methodology includes stereocontrolled Michael-type reaction, functional group adjustements and Wittig olefination. Copyright (C) 1996 Elsevier Science Ltd
• Total synthesis of five natural eremophilane-type sesquiterpenoids
  作者：Zhe Meng、Bo Liu

  DOI：10.1039/c7ob02769a

  日期：——

  The first total syntheses of five natural eremophilane-type sesquiterpenoids were achieved in 4–12 steps via a common synthetic intermediate. The syntheses feature a double Michael addition, Robinson annulation, α-enolization of an unsaturated ketone, and Pd-catalyzed Suzuki coupling reaction to install the side chain. This synthetic strategy could be easily extended to other eremophilane-type sesquiterpenoids

  通过一个普通的合成中间体，在4至12个步骤中完成了5种天然艾草双酚倍半萜类化合物的第一个总合成。合成具有双迈克尔加成反应，罗宾逊环化，不饱和酮的α-烯丙基化和Pd催化的Suzuki偶联反应以安装侧链。这种合成策略可以很容易地扩展到其他具有类似双环骨架的天青石型倍半萜。