(S)-3-methyl-2-methylenecyclohexanone | 124482-30-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-3-methyl-2-methylenecyclohexanone
• 英文别名: (3S)-3-methyl-2-methylidenecyclohexan-1-one
• CAS: 124482-30-0
• 化学式: C₈H₁₂O
• 分子量: 124.183
• InChiKey: NWFXCNZMWSBSDE-LURJTMIESA-N

物化性质

• 沸点：
  192.2±10.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 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：

  (S)-3-methyl-2-methylenecyclohexanone 在 palladium on activated charcoal 三丁基膦 、 氢气 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 23.0h， 生成 tert-butyl (2S,5S,10S)-10-methyl-6-oxo-spiro[4.5]decane-2-carboxylate
  参考文献：
  名称：

  一种膦催化的[3 + 2]环加成策略，导致首次合成（-）-海因溶胶。

  摘要：

  第一步，通过膦催化2,3-丁二烯酸叔丁酯或2-丁酸叔丁酯与3-甲基-2-亚甲基环己酮的膦酸酯催化的[3 + 2]环加成反应，构建了具有高立体选择性的顺式螺维酮骨架。（5 ）。这种方法以自然产物（-）-海因索尔的第一个高效的全合成为例，后者是脑循环和代谢改善剂的活性成分。

  DOI：

  10.1021/jo034281f
• 作为产物：
  描述：

  2-(硝基甲基)-环己-1-烯-3-酮 在 lithium bromide 作用下， 以 乙腈 为溶剂， 反应 2.17h， 生成 (S)-3-methyl-2-methylenecyclohexanone
  参考文献：
  名称：

  Asymmetric synthesis of 3-substituted 2-exo-methylenealkanones by addition-elimination reaction using a chiral leaving group and organometallic nucleophiles

  摘要：

  A novel diastereodifferentiating addition-elimination reaction of (S)-2-[[2-(methoxymethyl)-1-pyrrolidinyl]methyl]-2-alken-1-ones with organometallic reagents such as organocuprates and organozincates afforded optically active 3-substituted 2-methylenealkanones with high enantiomeric purity. The enantiomeric excess (ee) of the products in this asymmetric induction reaction involving 1,5-transfer of stereogenicity was highly dependent on the structure of the enone substrates and the type of organometallic reagents, chiral auxiliaries, and added Lewis acids: (i) the use of lithium diorganocuprates (R2CuLi) led to the highest ee's, (ii) in the reaction with R2CuLi the ee decreased in the following order by varying their structure of the main framework of the enones, cycloheptenones (96-97% ee) > cyclohexenones (95% ee) > cyclopentenones (82-85% ee) > acyclic enones (55-70% ee), (iii) the addition of LiBr as the external Lewis acid in the reaction with R2CuLi did not affect the ee, whereas that of ZnBr2 or MgBr2 decreased the ee by 5% or considerably more, respectively, and (iv) the existence of the methoxy oxygen atom in the chiral auxiliary was essential to achieve high ee's. The origin of the observed high and low ee's was rationalized by considering plausible transition state models.

  DOI：

  10.1021/jo00044a026

文献信息

• Asymmetric synthesis of 3-substituted-2-exo-methylenecyclohexanones via 1,5-diastereoselection by using a chiral amine
  作者：Rui Tamura、Kenichiro Watabe、Hitoshi Katayama、Hitomi Suzuki、Yukio Yamamoto

  DOI：10.1021/jo00289a003

  日期：1990.1
• TAMURA, RUI;WATABE, KEN-ICHIRO;KATAYAMA, HITOSHI;SUZUKI, HITOMI;YAMAMOTO,+, J. ORG. CHEM., 55,(1990) N, C. 408-410
  作者：TAMURA, RUI、WATABE, KEN-ICHIRO、KATAYAMA, HITOSHI、SUZUKI, HITOMI、YAMAMOTO,+

  DOI：——

  日期：——
• Asymmetric synthesis of 3-substituted 2-exo-methylenealkanones by addition-elimination reaction using a chiral leaving group and organometallic nucleophiles
  作者：Rui Tamura、Kenichiro Watabe、Noboru Ono、Yukio Yamamoto

  DOI：10.1021/jo00044a026

  日期：1992.8

  A novel diastereodifferentiating addition-elimination reaction of (S)-2-[[2-(methoxymethyl)-1-pyrrolidinyl]methyl]-2-alken-1-ones with organometallic reagents such as organocuprates and organozincates afforded optically active 3-substituted 2-methylenealkanones with high enantiomeric purity. The enantiomeric excess (ee) of the products in this asymmetric induction reaction involving 1,5-transfer of stereogenicity was highly dependent on the structure of the enone substrates and the type of organometallic reagents, chiral auxiliaries, and added Lewis acids: (i) the use of lithium diorganocuprates (R2CuLi) led to the highest ee's, (ii) in the reaction with R2CuLi the ee decreased in the following order by varying their structure of the main framework of the enones, cycloheptenones (96-97% ee) > cyclohexenones (95% ee) > cyclopentenones (82-85% ee) > acyclic enones (55-70% ee), (iii) the addition of LiBr as the external Lewis acid in the reaction with R2CuLi did not affect the ee, whereas that of ZnBr2 or MgBr2 decreased the ee by 5% or considerably more, respectively, and (iv) the existence of the methoxy oxygen atom in the chiral auxiliary was essential to achieve high ee's. The origin of the observed high and low ee's was rationalized by considering plausible transition state models.
• A Phosphine-Catalyzed [3+2] Cycloaddition Strategy Leading to the First Total Synthesis of (−)-Hinesol
  作者：Yishu Du、Xiyan Lu

  DOI：10.1021/jo034281f

  日期：2003.8.1

  cis-spirovetivanes was constructed with high stereoselectivity by the phosphine-catalyzed [3+2] cycloaddition reaction of tert-butyl 2,3-butadienoate or 2-butynoate with 3-methyl-2-methylenecyclohexanone (5). This method was exemplified by the first highly efficient total synthesis of natural product (-)-hinesol, which is an active ingredient of cerebral circulation and metabolism improvers.

  第一步，通过膦催化2,3-丁二烯酸叔丁酯或2-丁酸叔丁酯与3-甲基-2-亚甲基环己酮的膦酸酯催化的[3 + 2]环加成反应，构建了具有高立体选择性的顺式螺维酮骨架。（5 ）。这种方法以自然产物（-）-海因索尔的第一个高效的全合成为例，后者是脑循环和代谢改善剂的活性成分。