(4S)-N-Methacryloyl-4-methyl-2-oxazolidinone | 148081-12-3

• 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)-N-Methacryloyl-4-methyl-2-oxazolidinone
• 英文别名: (4S)-4-methyl-3-(2-methylprop-2-enoyl)-1,3-oxazolidin-2-one
• CAS: 148081-12-3
• 化学式: C₈H₁₁NO₃
• 分子量: 169.18
• InChiKey: VHJNVVAGPBYMRR-LURJTMIESA-N

物化性质

• 沸点：
  226.2±23.0 °C(Predicted)
• 密度：
  1.155±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  甲醇 、 (4S)-N-Methacryloyl-4-methyl-2-oxazolidinone 在 氧气 、 copper(l) chloride 、 palladium dichloride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 29.0h， 以61%的产率得到
  参考文献：
  名称：

  Palladium(II)-catalysed asymmetric acetalization of alkenes

  摘要：

  以 4-叔丁基恶唑烷-2-酮为手性助剂的甲基丙烯酰胺在 PdCl2 催化剂存在下与甲醇反应，生成 95% 非对映异构过量的相应缩醛，去除助剂后形成手性缩醛。

  DOI：

  10.1039/c39930000117
• 作为产物：
  描述：

  (4S)-4-甲基-2-噁唑烷酮 、 甲基丙烯酰氯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以65%的产率得到(4S)-N-Methacryloyl-4-methyl-2-oxazolidinone
  参考文献：
  名称：

  Palladium(II)-catalyzed asymmetric acetalization of alkenes

  摘要：

  The terminal olefinic carbon of N-methacryloyl-2-oxazolidinones is smoothly acetalized by alcohols in the presence of PdCl2 catalyst. The use of 4(S)-isopropyl-, phenyl-, and tert-butyl-2-oxazolidinones as the chiral auxiliary resulted in the formation of the corresponding (2'S)-acetals in 61, 80, and 95% de, respectively. Reductive removal of the auxiliary with LiAlH4 followed by deacetalization produced (R)-3-hydroxy-2-methylpropanal. The enantiomer of this compound, derived from 4(R)substituted oxazolidinones, served as a building block for synthesizing a 1 beta-methylcarbapenem precursor in high enantiomeric excess. In the acetalization of 3',3'-dideuteriated methacryloyl-4-isopropyloxaiolidinone with MeOH, one D-atom on the terminal olefinic carbon stereoselectively migrated to the chiral center in the product acetal. On the basis of this 1,2-hydride migration and the conformational preference of the methacryloyl moiety, the reaction pathway and the mechanism of the diastereoselection are discussed.

  DOI：

  10.1021/jo00124a032

文献信息

• Palladium(II)-catalyzed asymmetric acetalization of alkenes
  作者：Takahiro Hosokawa、Toshio Yamanaka、Motohiro Itotani、Shun-Ichi Murahashi

  DOI：10.1021/jo00124a032

  日期：1995.9

  The terminal olefinic carbon of N-methacryloyl-2-oxazolidinones is smoothly acetalized by alcohols in the presence of PdCl2 catalyst. The use of 4(S)-isopropyl-, phenyl-, and tert-butyl-2-oxazolidinones as the chiral auxiliary resulted in the formation of the corresponding (2'S)-acetals in 61, 80, and 95% de, respectively. Reductive removal of the auxiliary with LiAlH4 followed by deacetalization produced (R)-3-hydroxy-2-methylpropanal. The enantiomer of this compound, derived from 4(R)substituted oxazolidinones, served as a building block for synthesizing a 1 beta-methylcarbapenem precursor in high enantiomeric excess. In the acetalization of 3',3'-dideuteriated methacryloyl-4-isopropyloxaiolidinone with MeOH, one D-atom on the terminal olefinic carbon stereoselectively migrated to the chiral center in the product acetal. On the basis of this 1,2-hydride migration and the conformational preference of the methacryloyl moiety, the reaction pathway and the mechanism of the diastereoselection are discussed.
• Palladium(II)-catalysed asymmetric acetalization of alkenes
  作者：Takahiro Hosokawa、Toshio Yamanaka、Shun-Ichi Murahashi

  DOI：10.1039/c39930000117

  日期：——

  Methacrylamide bearing 4-tert-butyloxazolidin-2-one as a chiral auxiliary reacts with methanol in the presence of PdCl2 catalyst to give the corresponding acetal in 95% diastereoisomeric excess, and removal of the auxiliary results in the formation of chiral acetals.

  以 4-叔丁基恶唑烷-2-酮为手性助剂的甲基丙烯酰胺在 PdCl2 催化剂存在下与甲醇反应，生成 95% 非对映异构过量的相应缩醛，去除助剂后形成手性缩醛。