(4S)-3-[(2S,3S)-2-bromo-3-(4-methoxyphenyl)butanoyl]-4-phenyl-1,3-oxazolidin-2-one | 148706-34-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (4S)-3-[(2S,3S)-2-bromo-3-(4-methoxyphenyl)butanoyl]-4-phenyl-1,3-oxazolidin-2-one
• CAS: 148706-34-7
• 化学式: C₂₀H₂₀BrNO₄
• 分子量: 418.287
• InChiKey: DWRRMBAWCLVJED-VHSSKADRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4S)-3-[(2S,3S)-2-bromo-3-(4-methoxyphenyl)butanoyl]-4-phenyl-1,3-oxazolidin-2-one 在 叠氮化四丁基铵 作用下， 以 乙腈 为溶剂， 反应 6.0h， 生成 (3(2R,3S),4S)-3-<2-Azido-3-(4-methoxyphenyl)butyroyl>-4-phenyl-2-oxazolidinone
  参考文献：
  名称：

  Efficient method for the total asymmetric synthesis of the isomers of .beta.-methyltyrosine

  摘要：

  Alpha-Amino acids modified at the beta-carbon atom can provide topographical constraints when incorporated into a peptide. Such modifications can modulate the physical, chemical, and biological properties of the compound. In order to properly evaluate the effect of such modifications, large-scale asymmetric syntheses of the isomers are needed. A method for the stereoselective large-scale synthesis of an four stereoisomers of beta-methyltyrosine is described in this paper. The stereochemistry of both the alpha- and beta-stereocenters was set using 4-phenyl-2-oxazolidinone as a chiral auxiliary. The key reactions were an asymmetric Michael-like addition of an organocuprate to a chiral alpha,beta-unsaturated acyloxazolidinone (beta center) and subsequent stereoselective electrophilic bromination of the resulting product (alpha center). Conversion of the bromide to the azide, catalyzed hydrolysis to the azido acid with simultaneous recovery of the chiral auxiliary, reduction of the azide, and final deprotection of the phenol group afforded the desired amino acids. In general, the reactions were performed in yields over 80 %, and the isomers were obtained in enantiomeric purities of 98:2 to 99:1.

  DOI：

  10.1021/jo00078a042
• 作为产物：
  描述：

  (4S)-N-crotonyl-4-phenyloxazolidin-2-one 在 N-溴代丁二酰亚胺(NBS) 、 三氟甲磺酸二丁硼 、 N,N-二异丙基乙胺 作用下， 反应 5.5h， 生成 (4S)-3-[(2S,3S)-2-bromo-3-(4-methoxyphenyl)butanoyl]-4-phenyl-1,3-oxazolidin-2-one
  参考文献：
  名称：

  Efficient method for the total asymmetric synthesis of the isomers of .beta.-methyltyrosine

  摘要：

  Alpha-Amino acids modified at the beta-carbon atom can provide topographical constraints when incorporated into a peptide. Such modifications can modulate the physical, chemical, and biological properties of the compound. In order to properly evaluate the effect of such modifications, large-scale asymmetric syntheses of the isomers are needed. A method for the stereoselective large-scale synthesis of an four stereoisomers of beta-methyltyrosine is described in this paper. The stereochemistry of both the alpha- and beta-stereocenters was set using 4-phenyl-2-oxazolidinone as a chiral auxiliary. The key reactions were an asymmetric Michael-like addition of an organocuprate to a chiral alpha,beta-unsaturated acyloxazolidinone (beta center) and subsequent stereoselective electrophilic bromination of the resulting product (alpha center). Conversion of the bromide to the azide, catalyzed hydrolysis to the azido acid with simultaneous recovery of the chiral auxiliary, reduction of the azide, and final deprotection of the phenol group afforded the desired amino acids. In general, the reactions were performed in yields over 80 %, and the isomers were obtained in enantiomeric purities of 98:2 to 99:1.

  DOI：

  10.1021/jo00078a042

文献信息

• Diastereospecific tandem Michael-like addition / electrophilic bromination: A one-pot tandem asymmetric synthesis of precursors of unusual amino acids
  作者：Guigen Li、Mark A. Jarosinski、Victor J. Hruby

  DOI：10.1016/s0040-4039(00)77625-8

  日期：1993.4

  A systematic series of key intermediates of unusual β-methyl-amino acids have been synthesized by using a modified Evans auxiliary in an asymmetric Michael-like reaction followed by direct bromination in a one-pot reaction.

  通过在不对称迈克尔样反应中使用修饰的Evans辅助剂，然后在单锅反应中直接溴化，合成了系统化的一系列非常规β-甲基氨基酸关键中间体。