(3S)-3-benzyl-5,5-dimethyloxolan-2-one | 175979-81-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (3S)-3-benzyl-5,5-dimethyloxolan-2-one
• CAS: 175979-81-4
• 化学式: C₁₃H₁₆O₂
• 分子量: 204.269
• InChiKey: PYHHNUZYJVNRMX-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3S)-3-benzyl-5,5-dimethyloxolan-2-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 (2S)-2-benzyl-4-methylpentane-1,4-diol
  参考文献：
  名称：

  Practical Syntheses of Enantiomerically Enriched γ-Lactones and γ-Hydroxy Ketones by the Alkylation of Pseudoephedrine Amides with Epoxides and Their Derivatives

  摘要：

  Pseudoephedrine amide enolates are shown to undergo efficient alkylation reactions with epoxides as electrophiles. Reactions with monosubstituted epoxides are subject to stereochemical matching such that the pairing leading to the 1,3-syn diastereomer is a highly selective, synthetically useful process, while the pairing forming the 1,3-anti diastereomer is not. Reactions with the 1,1-disubstituted epoxide isobutylene oxide are also highly diastereoselective and synthetically useful, but ethylene oxide exhibits poor diastereoselectivity. As an alternative to the use of ethylene oxide, 2-(tert-butyldimethylsilyloxy)ethyl iodide is shown to undergo highly diastereoselective and efficient alkylation reactions with pseudoephedrine amide enolates. Interestingly, epoxides and alkyl halides are found to attack opposite pi-faces of pseudoephedrine amide enolates. The products of each of these alkylation reactions are transformed efficiently into gamma-lactones by acidic hydrolysis and into methyl ketones by the addition of methyllithium. The methodology described provides useful procedures for the synthesis of enantiomerically enriched gamma-lactones and gamma-hydroxy ketones.

  DOI：

  10.1021/jo952032o
• 作为产物：
  描述：

  N-((1S,2S)-1-hydroxy-1-phenylpropan-2-yl)-N-methyl-3-phenylpropanamide 在 硫酸 、 lithium chloride 、 lithium diisopropyl amide 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 6.0h， 生成 (3S)-3-benzyl-5,5-dimethyloxolan-2-one
  参考文献：
  名称：

  Practical Syntheses of Enantiomerically Enriched γ-Lactones and γ-Hydroxy Ketones by the Alkylation of Pseudoephedrine Amides with Epoxides and Their Derivatives

  摘要：

  Pseudoephedrine amide enolates are shown to undergo efficient alkylation reactions with epoxides as electrophiles. Reactions with monosubstituted epoxides are subject to stereochemical matching such that the pairing leading to the 1,3-syn diastereomer is a highly selective, synthetically useful process, while the pairing forming the 1,3-anti diastereomer is not. Reactions with the 1,1-disubstituted epoxide isobutylene oxide are also highly diastereoselective and synthetically useful, but ethylene oxide exhibits poor diastereoselectivity. As an alternative to the use of ethylene oxide, 2-(tert-butyldimethylsilyloxy)ethyl iodide is shown to undergo highly diastereoselective and efficient alkylation reactions with pseudoephedrine amide enolates. Interestingly, epoxides and alkyl halides are found to attack opposite pi-faces of pseudoephedrine amide enolates. The products of each of these alkylation reactions are transformed efficiently into gamma-lactones by acidic hydrolysis and into methyl ketones by the addition of methyllithium. The methodology described provides useful procedures for the synthesis of enantiomerically enriched gamma-lactones and gamma-hydroxy ketones.

  DOI：

  10.1021/jo952032o

文献信息

• Enantioselective alkylation of lactams and lactones via lithium enolate formation using a chiral tetradentate lithium amide in the presence of lithium bromide
  作者：Jun-ichi Matsuo、Shu Kobayashi、Kenji Koga

  DOI：10.1016/s0040-4039(98)02235-7

  日期：1998.12

  Enantioselective alkylation of lactams and lactones can be realized up to 98% ee by deprotonation with a chiral tetradentate lithium amide (4b) in the presence of lithium bromide, and subsequent alkylation with active alkylating agents in non-chelating solvents.

  内酰胺和内酯的对映选择性烷基化可通过在溴化锂的存在下用手性四齿氨基酰胺锂（4b）使质子去质子化，然后在非螯合剂中用活性烷基化剂进行烷基化来实现高达98％ee 。