2,3-dimethylcyclohexanone | 234078-11-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-dimethylcyclohexanone
• 英文别名: (3R)-2,3-dimethylcyclohexanone；(3R)-2,3alpha-Dimethylcyclohexane-1-one；(3R)-2,3-dimethylcyclohexan-1-one
• CAS: 234078-11-6
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: OZCVOEUWYVVVME-ULUSZKPHSA-N

物化性质

• 沸点：
  176.8±8.0 °C(Predicted)
• 密度：
  0.882±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  2,3-dimethylcyclohexanone 在 三甲基氯硅烷 吡啶 、 sodium tetrahydroborate 、 正丁基锂 、 cerium(III) chloride 、 lithium carbonate 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 magnesium bromide ethyl etherate 、 甲基磺酰氯 、 三乙胺 、 二异丙胺 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 、 三氟乙酸酐 、 lithium chloride 、 lithium bromide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 Petroleum ether 为溶剂， 反应 80.16h， 生成 (4S,5R)-2-bromo-3-methoxymethoxymethyl-4,5-dimethyl-4-vinylcyclohex-2-enone
  参考文献：
  名称：

  Total Synthesis of (+)-Phomactin A Using a B-Alkyl Suzuki Macrocyclization

  摘要：

  A total synthesis of (+)-phomactin A is described using a B-alkyl Suzuki macrocyclization to incorporate the isolated trisubstituted olefin. This macrocyclization was accomplished with the sensitive hydrated furan ring in place. (R)-(+)-pulegone was used to establish the highly substituted cyclohexene core of the molecule.

  DOI：

  10.1021/ja0296531
• 作为产物：
  描述：

  (R)-6-Isopropylidene-2,3-dimethyl-cyclohexanone 在 氢氧化钾 作用下， 以 甲醇 、 水 为溶剂， 生成 2,3-dimethylcyclohexanone
  参考文献：
  名称：

  Tori, Motoo; Uchida, Naomi; Sumida, Aya, Journal of the Chemical Society. Perkin transactions I, 1995, # 12, p. 1513 - 1518

  摘要：

  DOI：

文献信息

• Total Synthesis and Structure Revision of Halioxepine
  作者：Caroline Poock、Markus Kalesse

  DOI：10.1002/chem.202004847

  日期：2021.1.21

  total synthesis of halioxepine is accomplished using a 1,4‐addition for constructing the quaternary center at C10 and a halo etherification for the generation of the tertiary ether at C7. The correct structure of halioxepine was determined by assembling different enantiomeric building blocks and by changing the relative configuration between C10 and C15.

  卤氧杂环己烷的首次全合成是通过 1,4 加成在 C10 处构建四级中心和卤代醚化在 C7 处生成叔醚来完成的。通过组装不同的对映体结构单元并改变 C10 和 C15 之间的相对构型，确定了卤氧杂平的正确结构。
• A Total Synthesis of (-)-Nardoaristolone B
  作者：Rohini S. Ople、Kishor L. Handore、Nidhi S. Kamat、D. Srinivasa Reddy

  DOI：10.1002/ejoc.201600538

  日期：2016.8

  stereoselective total synthesis of (–)-Nardoaristolone B, a nor-aristolane sesquiterpenoid natural product with an unusual 3/5/6 tricyclic ring system is described. The highlights of the present work includes use of (+)-(R)-Pulegone as a chiral-pool starting material, ring-closing metathesis, allylic oxidation and stereoselective cyclopropanation. In addition, a new analogue of Nardoaristolone B (minor product

  描述了 (-)-Nardoaristolone B 的立体选择性全合成，它是一种具有不寻常的 3/5/6 三环系统的去甲马兜铃倍半萜类天然产物。目前工作的亮点包括使用 (+)-(R)-Pulegone 作为手性池起始材料、闭环复分解、烯丙基氧化和立体选择性环丙烷化。此外，Nardoaristolone B 的新类似物（来自最后一步的次要产物）以纯形式分离出来，并在单晶 X 射线分析的帮助下进行了充分表征。
• 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。
• Total Syntheses of Anominine and Tubingensin A
  作者：Ming Bian、Zhen Wang、Xiaochun Xiong、Yu Sun、Carlo Matera、K. C. Nicolaou、Ang Li

  DOI：10.1021/ja302765m

  日期：2012.5.16

  A divergent strategy for the total syntheses of the indole terpenoid anominine (1) and its natural congener tubingensin A (2) has been developed. The common intermediate 11 bearing all of the required stereogenic centers for both natural products was first assembled by employing a Ueno-Stork radical cyclization and a Sc(OTf)(3)-mediated Mukaiyama aldol reaction to form the key C-C bonds in a stereocontrolled manner. The route to anominine features a radical deoxygenation followed by an efficient side-chain installation, while the path to tubingensin A exploits a CuOTf-promoted 6 pi-electrocyclization/aromatization sequence to forge the central region of the pentacyclic scaffold.
• Total synthesis of optically active liverwort sesquiterpenes, trifarienols A and B, using phenylethylamine as a chiral auxiliary
  作者：Motoo Tori、Kenji Hisazumi、Tomonari Wada、Masakazu Sono、Katsuyuki Nakashima

  DOI：10.1016/s0957-4166(99)00067-1

  日期：1999.3

  The imine of (rac)-2,3-dimethylcyclohexanone 10a with (S)-(-)-phenylethylamine was reacted with methyl acrylate to yield methyl (1'S,6'R)-3-(1',6'-dimethyl-2'-oxocyclohexyl)propanoate 4a in 26% (97% eel)after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b, was used, the same product 4b was obtained in 59% yield (>99.5% ee) after hydrolysis. When (2RS,3R)-2,3-dimethylcyclohexanone 10b and (R)-(+)-phenylethylamine were used, the reaction underwent in only 5% yield, the products being 4c, 12, 13, 14, and 15. Thus, the reaction of 3b with methyl acrylate is a matched case, while that of 3c is a mismatched case. These phenomena are explained by the nonbonded interaction of methyl acrylate with chiral phenylethylamine and the methyl group at the 6'-position of the cyclohexanone ring in the transition state. The propanoate product 4b was successfully transformed into liverwort sesquiterpene (+)-trifarienol A 1 and (-)-trifarienol B 2 in 10 steps. We have developed an HPLC method to determine the ees of 2,2-disubstituted and 2,2,3-trisubstituted cyclohexanones using the corresponding pentafluorophenyl esters. (C) 1999 Elsevier Science Ltd. All rights reserved.