甲基丙烯酸甲酯-D2 | 55063-97-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 甲基丙烯酸甲酯-D2
• 英文名称: methyl<β-(2)H2>methacrylate
• 英文别名: methyl methacrylate-3,3-d2；3,3-dideuterio-2-methyl-acrylic acid methyl ester；methyl 3,3-dideuterio-2-methylprop-2-enoate
• CAS: 55063-97-3
• 化学式: C₅H₈O₂
• 分子量: 102.101
• InChiKey: VVQNEPGJFQJSBK-DICFDUPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  甲基丙烯酸甲酯-D2 在 lithium hydroxide 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 24.0h， 以53%的产率得到1,2-d2-Methyl methacrylate
  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：

  甲醛-d2 、 3-甲氧基-2-甲基-3-氧代丙酸 在 二乙胺 作用下， 以 重水 为溶剂， 反应 40.0h， 以63%的产率得到甲基丙烯酸甲酯-D2
  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

• Organocatalytic Tail-to-Tail Dimerization of Olefin: Umpolung of Methyl Methacrylate Mediated by N-Heterocyclic Carbene
  作者：Shin-ichi Matsuoka、Yoshiya Ota、Atsushi Washio、Akiho Katada、Kenji Ichioka、Koji Takagi、Masato Suzuki

  DOI：10.1021/ol201380m

  日期：2011.7.15

  Highly selective tail-to-tall dimerization of methyl methacrylate has been realized by an N-heterocyclic carbene catalyst, giving dimethyl 2,5-dimethyl-2-hexenedioate with an E/Z ratio of 95:5 in 86% isolated yield. The umpolung mechanism Is proposed on the basis of Interception of the intermediates using ESI-MS analyses and deuterium-labeling experiments.
• Lane, Jeremy; Tabner, Brian J., Journal of the Chemical Society. Perkin transactions II, 1985, p. 1665 - 1668
  作者：Lane, Jeremy、Tabner, Brian J.

  DOI：——

  日期：——
• 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.