(R)-2-Benzo[1,3]dioxol-5-ylmethyl-2-methyl-malonamic acid | 159835-32-2

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: (R)-2-Benzo[1,3]dioxol-5-ylmethyl-2-methyl-malonamic acid
• CAS: 159835-32-2
• 化学式: C₁₂H₁₃NO₅
• 分子量: 251.239
• InChiKey: MDQWCDFEEDOCQV-GFCCVEGCSA-N

物化性质

• 沸点：
  492.6±45.0 °C(predicted)
• 密度：
  1.408±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.53
• 重原子数：
  18.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  98.85
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (R)-2-Benzo[1,3]dioxol-5-ylmethyl-2-methyl-malonamic acid 在 溴 、 sodium methylate 作用下， 生成 (S)-3-Benzo[1,3]dioxol-5-yl-2-methoxycarbonylamino-2-methyl-propionic acid methyl ester
  参考文献：
  名称：

  Realization of the synthesis of α,α-disubstituted carbamylacetates and cyanoacetates by either enzymatic or chemical functional group transformation, depending upon the substrate specificity of Rhodococcus amidase

  摘要：

  Substrate specificity and enantioselectivity of nitrile hydratase and amidase from R. rhodochrous IFO 15564 has been studied by applying a series of alpha,alpha-disubstituted malononitriles and related substrates. The amidase preferentially hydrolyzed the pro-(R) carbamyl group (amide) of the prochiral diamides, an intermediate resulting from the action of nitrile hydratase in a nonenantiotopic group-selective manner. The introduction of a fluorine atom at the alpha-position caused an inhibitory effect on amidase. By a combination of this microbial transformation and the subsequent Hofmann rearrangement, an important precursor of (S)methyldopa with 98.4% ee has been prepared. For the enzymatically poor substrate, the action on HO3SONO-H2O on the carbamyl group was effective, leaving the cyano group intact. This conversion is demonstrated as the key step for the expeditious preparation of (+/-)-alpha-cyano-alpha-fluoro-alpha-phenylacetic acid (CFPA) from diethyl alpha-fluoro-alpha-phenylmalonate. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.047
• 作为产物：
  描述：

  2-Benzo[1,3]dioxol-5-ylmethyl-2-methyl-malononitrile 在 Rhodococcus rhodochrous IFO 15564 cells 作用下， 反应 72.0h， 以95%的产率得到(R)-2-Benzo[1,3]dioxol-5-ylmethyl-2-methyl-malonamic acid
  参考文献：
  名称：

  Realization of the synthesis of α,α-disubstituted carbamylacetates and cyanoacetates by either enzymatic or chemical functional group transformation, depending upon the substrate specificity of Rhodococcus amidase

  摘要：

  Substrate specificity and enantioselectivity of nitrile hydratase and amidase from R. rhodochrous IFO 15564 has been studied by applying a series of alpha,alpha-disubstituted malononitriles and related substrates. The amidase preferentially hydrolyzed the pro-(R) carbamyl group (amide) of the prochiral diamides, an intermediate resulting from the action of nitrile hydratase in a nonenantiotopic group-selective manner. The introduction of a fluorine atom at the alpha-position caused an inhibitory effect on amidase. By a combination of this microbial transformation and the subsequent Hofmann rearrangement, an important precursor of (S)methyldopa with 98.4% ee has been prepared. For the enzymatically poor substrate, the action on HO3SONO-H2O on the carbamyl group was effective, leaving the cyano group intact. This conversion is demonstrated as the key step for the expeditious preparation of (+/-)-alpha-cyano-alpha-fluoro-alpha-phenylacetic acid (CFPA) from diethyl alpha-fluoro-alpha-phenylmalonate. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.04.047