threo-D-(2R,3S)-β-Methyltyrosine | 128573-11-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: threo-D-(2R,3S)-β-Methyltyrosine
• 英文别名: threo(2R,3S)-D-β-methyltyrosine；(2R,3S)-2-Amino-3-(4-hydroxy-phenyl)-butyric acid；(2R,3S)-2-amino-3-(4-hydroxyphenyl)butanoic acid
• CAS: 128573-11-5
• 化学式: C₁₀H₁₃NO₃
• 分子量: 195.218
• InChiKey: CSKLNJOBXITXRM-IMTBSYHQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1.4
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  83.6
• 氢给体数：
  3
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-methoxytrifluoromethylphenylacetyl chloride 、 threo-D-(2R,3S)-β-Methyltyrosine 、 仲丁醇 在 盐酸 、 三乙胺 作用下， 生成 (2R,3S,2'S)-N,O-Bis<2-(trifluoromethyl)-2-methoxyphenylacetyl>-β-methyltyrosine isobutyl ester
  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：

  (3(3R),4S)-3-<3-(4'-Methoxyphenyl)butanoyl>-4-phenyl-2-oxazolidinone 在 palladium on activated charcoal 盐酸 、 lithium hydroxide 、 N-溴代丁二酰亚胺(NBS) 、 三氟甲磺酸二丁硼 、 氢溴酸 、 氢气 、 双氧水 、 叠氮化四丁基铵 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 溶剂黄146 、 乙腈 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 33.25h， 生成 threo-D-(2R,3S)-β-Methyltyrosine
  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

• Asymmetric synthesis of unusual amino acids: Synthesis of optically pure isomers of β-methyltyrosine
  作者：Ernesto Nicolas、Ramalinga Dharanipragada、Geza Toth、Victor J Hruby

  DOI：10.1016/s0040-4039(01)93367-2

  日期：1989.1

  Synthesis of optically pure isomers of β-methyltyrosine has been accomplished.

  β-甲基酪氨酸的光学纯异构体的合成已经完成。
• NICOLAS, ERNESTO;DHARANIPRAGADA, RAMALINGA;TOTH, GEZA;HRURBY, VICTOR J., TETRAHEDRON LETT., 30,(1989) N9, C. 6845-6848
  作者：NICOLAS, ERNESTO、DHARANIPRAGADA, RAMALINGA、TOTH, GEZA、HRURBY, VICTOR J.

  DOI：——

  日期：——
• Efficient method for the total asymmetric synthesis of the isomers of .beta.-methyltyrosine
  作者：Ernesto Nicolas、K. C. Russell、J. Knollenberg、Victor J. Hruby

  DOI：10.1021/jo00078a042

  日期：1993.12

  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.