(4S,5R)-4-benzyl-5-((Z)hex-1-enyl)oxazolidin-2-one | 484021-01-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: (4S,5R)-4-benzyl-5-((Z)hex-1-enyl)oxazolidin-2-one
• 英文别名: (4S,5R)-4-benzyl-5-[(Z)-hex-1-enyl]-1,3-oxazolidin-2-one
• CAS: 484021-01-4
• 化学式: C₁₆H₂₁NO₂
• 分子量: 259.348
• InChiKey: AMQFXZIPWAFVAO-COFUAWPYSA-N

物化性质

• 沸点：
  441.9±25.0 °C(Predicted)
• 密度：
  1.098±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  38.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4S,5R)-4-benzyl-5-((Z)hex-1-enyl)oxazolidin-2-one 在 一氧化碳 、 (Ph₃P)PdCl₂ 作用下， 以 乙醇 为溶剂， 60.0~100.0 ℃ 、6.59 MPa 条件下， 反应 96.0h， 生成 (3S,6S)-6-benzyl-3-butyl-3,6-dihydro-1H-pyridin-2-one
  参考文献：
  名称：

  Diastereospecific carbonylation of π-allylpalladium complexes to give 3,6-disubstituted 3,6-dihydro-1H-pyridin-2-ones

  摘要：

  (Ph3P)(2)PdCl2 was found to be the most effective of a range of catalysts for decarboxylative carbonylation of (4S,5RS)-5-ethenyl-4-(2-propyl)oxazolidin-2-one to give the delta-lactam, (6S)-3,6-dihydro-6-(2-propyl)-1H-pyridin-2-one. In a similar way, diastereoisomerically pure (4S,5S)-4-benzyl-5-((Z)alk-1-enyl)oxazolidin-2-ones undergo stereospecific carbonylation to give (3R,6S)-6-benzyl-3-alkyl-3,6-dihydro-1H-pyridin-2-ones. The diastereoisomeric (4S,5R)-4-benzyl-5-((Z)alk-1-enyl)oxazolidin-2-ones give rise to a separable mixture of the corresponding (3S,6S)-6-benzyl-3-alkyl-3,6-dihydro-1H-pyridin-2-one and (4S,5S)-4-benzyl-5-((E)alk-1-enyl)oxazolidin-2-one. Under more forcing conditions, the latter oxazolidinone is carbonylated to the 3,6-anti-pyridinone. The stereochemical course of the reactions can be rationalized by formation of a pi-allyl palladium cation with inversion of configuration followed by carbonylation with retention. The stereospecificity observed in our system precludes metal-metal exchange of the pi-allyl complexes by a Pd(0) displacement process. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00683-x
• 作为产物：
  描述：

  (4S)-4-benzyl-5-(hex-1-ynyl)oxazolidin-2-one 在 喹啉 、 Lindlar's catalyst 、 氢气 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以68%的产率得到(4S,5S)-4-benzyl-5-((Z)hex-1-enyl)oxazolidin-2-one
  参考文献：
  名称：

  Diastereospecific carbonylation of π-allylpalladium complexes to give 3,6-disubstituted 3,6-dihydro-1H-pyridin-2-ones

  摘要：

  (Ph3P)(2)PdCl2 was found to be the most effective of a range of catalysts for decarboxylative carbonylation of (4S,5RS)-5-ethenyl-4-(2-propyl)oxazolidin-2-one to give the delta-lactam, (6S)-3,6-dihydro-6-(2-propyl)-1H-pyridin-2-one. In a similar way, diastereoisomerically pure (4S,5S)-4-benzyl-5-((Z)alk-1-enyl)oxazolidin-2-ones undergo stereospecific carbonylation to give (3R,6S)-6-benzyl-3-alkyl-3,6-dihydro-1H-pyridin-2-ones. The diastereoisomeric (4S,5R)-4-benzyl-5-((Z)alk-1-enyl)oxazolidin-2-ones give rise to a separable mixture of the corresponding (3S,6S)-6-benzyl-3-alkyl-3,6-dihydro-1H-pyridin-2-one and (4S,5S)-4-benzyl-5-((E)alk-1-enyl)oxazolidin-2-one. Under more forcing conditions, the latter oxazolidinone is carbonylated to the 3,6-anti-pyridinone. The stereochemical course of the reactions can be rationalized by formation of a pi-allyl palladium cation with inversion of configuration followed by carbonylation with retention. The stereospecificity observed in our system precludes metal-metal exchange of the pi-allyl complexes by a Pd(0) displacement process. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(02)00683-x