1,1-d2-Methacryloyl chloride

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 酰卤
• 英文名称: 1,1-d2-Methacryloyl chloride
• 英文别名: 3,3-Dideuterio-2-methylprop-2-enoyl chloride
• 化学式: C₄H₅ClO
• 分子量: 106.52
• InChiKey: VHRYZQNGTZXDNX-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.25
• 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)-4-异丙基-2-唑烷酮 、 1,1-d2-Methacryloyl chloride 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 3,3'-d2-(4S)-N-Methacryloyl-4-isopropyl-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
• 作为产物：
  描述：

  1,2-d2-Methyl methacrylate 在 草酰氯 、 N,N-二甲基甲酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 1,1-d2-Methacryloyl chloride
  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