methyl (R)-1-allyl-2-oxocyclohexanecarboxylate | 89708-65-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (R)-1-allyl-2-oxocyclohexanecarboxylate
• 英文别名: methyl (1R)-2-oxo-1-prop-2-enylcyclohexane-1-carboxylate
• CAS: 89708-65-6
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: OURWLCPHOKLVAJ-NSHDSACASA-N

物化性质

• 沸点：
  262.9±33.0 °C(Predicted)
• 密度：
  1.042±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl (R)-1-allyl-2-oxocyclohexanecarboxylate 、 sodium ethanolate 生成 ethyl (R)-1-allyl-2-oxocyclohexane-1-carboxylate
  参考文献：
  名称：

  TOMIOKA, KIYOSHI;ANDO, KAORI;TAKEMASA, YUTAKA;KOGA, KENJI, J. AMER. CHEM. SOC., 1984, 106, N 9, 2718-2719

  摘要：

  DOI：
• 作为产物：
  描述：

  methyl (1S)-1-allyl-2-<(1S,2S)-2-hydroxycyclohexan-1-yl>oxy-1-methyl-2-cyclohexen-1-carboxylate 在 甲醇 、 三氟化硼乙醚 、 水 作用下， 生成 methyl (R)-1-allyl-2-oxocyclohexanecarboxylate
  参考文献：
  名称：

  Asymmetric alkylation using chiral cyclic diols to prepare a quaternary carbon

  摘要：

  Asymmetric alkylation of cyclic and acyclic beta-keto ester acetals (4, 5, 13, 14, and 18) with C-2-symmetric cycloalkane-1,2-dioxy moiety proceeded in a highly diastereoselective manner to afford enol ethers (9-12, 15-17, 19a-c) with a chiral quaternary carbon.

  DOI：

  10.1016/s0040-4020(01)87012-5

文献信息

• Enantioselective Palladium-Catalyzed Decarboxylative Allylation of β-Keto Esters Assisted by a Thiourea
  作者：Lung Chung、Xumu Zhang、Hua Qian、Guoxian Gu、Qinghai Zhou、Jiaxiang Lu

  DOI：10.1055/s-0036-1590869

  日期：2018.1

  decarboxylative allylation of β-keto esters catalyzed by a palladium bis(phosphine)-thiourea complex is reported. This procedure is not only effective for β-keto esters, but also effective for β-keto amides. An intermolecular variant of the asymmetric decarboxylative allylation is also established. DFT calculations indicate that an outer-sphere mechanism is viable for the decarboxylative allylation

  报道了由钯双（膦）-硫脲复合物催化的 β-酮酯的对映选择性分子内脱羧烯丙基化。该程序不仅对β-酮酯有效，而且对β-酮酰胺有效。还建立了不对称脱羧烯丙基化的分子间变体。DFT 计算表明，外球机制对于 β-酮酯的脱羧烯丙基化是可行的。
• Asymmetric alkylation of .alpha.-alkyl .beta.-keto esters
  作者：Kiyoshi Tomioka、Kaori Ando、Yutaka Takemasa、Kenji Koga

  DOI：10.1021/ja00321a050

  日期：1984.5

  Diastereoselective alkylation de lithio enamines obtenues a partir d'α-alkyl β-cetoesters et du (S)-valinate de t-butyle

  非对映选择性烷基化脱硫烯胺减少部分 d'α-烷基 β-cetoesters et du (S)-valinate de t-butyle
• Factors controlling the diastereoface selectivity in the complementary asymmetric alkylation of α-alkyl β-keto esters
  作者：Kiyoshi Tomioka、Kaori Ando、Yutaka Takemasa、Kenji Koga

  DOI：10.1016/s0040-4039(01)91410-8

  日期：1984.1

  Complementary asymmetric alkylation reaction of the lithioenamine derived from 2-methoxycarbonylcyclohexanone and (S)-valine tert-butyl ester was examined by employing the various electron pair donating additives in a toluene solvent, in order to clarify the factors controlling the diastereoface selectivity.

  为了阐明控制非对映异构体选择性的因素，通过在甲苯溶剂中使用各种给电子对添加剂，研究了衍生自2-甲氧基羰基环己酮和（S）-缬氨酸叔丁基酯的硫代亚胺的互补不对称烷基化反应。
• Enantioselective Synthesis of [ <i>b</i> ]‐Annulated Azepane Scaffolds
  作者：Enno Aeissen、Aaron R. von Seggern、Marc Schmidtmann、Jens Christoffers

  DOI：10.1002/ejoc.202300180

  日期：——

  Optically active α-allyl-β-oxoesters are submitted to olefin cross metathesis and subsequent exhaustive hydrogenation and reductive amination to furnish [b]-annulated azepane derivatives.

  光学活性 α-烯丙基-β-氧代酯经过烯烃交叉复分解和随后的彻底氢化和还原胺化以提供 [ b ]-环氮杂环庚烷衍生物。
• Stereoselective reactions. XXI. Asymmetric alkylation of α-alkyl β-keto esters to α,α-dialkyl β-keto esters having either (R)- or (S)-chiral quaternary center depending on the solvent system
  作者：Kaori Ando、Yataka Takemasa、Kiyoshi Tomioka、Kenji Koga

  DOI：10.1016/s0040-4020(01)80346-x

  日期：——

  Asymmetric alkylation reaction of chiral enamines prepared from alpha-alkyl beta-keto esters and (S)-valine tert-butyl ester leading to either enantiomer is described. Lithiated chiral enamines can be alkylated with alkyl halides in a toluene solvent in the presence of HMPA to give, after hydrolysis, alpha,alpha-dialkyl beta-keto esters in 70-99%ee. The reactions in the presence of THF, dioxolane, or trimethylamine. instead of HMPA, afford the corresponding antipodes with enantiomeric purities of 44-92%ee. The present method provides a procedure for the synthesis of both enantiomers of alpha,alpha-dialkyl beta-keto esters in high enantiomeric purities starting from the same chiral enamines.