(2S,3S)-2,3-dimethylphenylalanine | 143837-86-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 苯丙酸
• 英文名称: (2S,3S)-2,3-dimethylphenylalanine
• 英文别名: (2S,3S)-2-amino-2-methyl-3-phenylbutanoic acid
• CAS: 143837-86-9
• 化学式: C₁₁H₁₅NO₂
• 分子量: 193.246
• InChiKey: JIJODEXUWUVDAU-KWQFWETISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  63.3
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 (2S,3S)-2,3-dimethylphenylalanine 在 盐酸 作用下， 反应 10.0h， 以72%的产率得到(3S,4S)-3,4-Dimethyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid
  参考文献：
  名称：

  New Amino Acids for the Topographical Control of Peptide Conformation: Synthesis of All the Isomers of .alpha.,.beta.-Dimethylphenylalanine and .alpha.,.beta.-Dimethyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic Acid of High Optical Purity

  摘要：

  The synthesis of all four diastereoisomers of alpha,beta-dimethylphenylalanine (4) as well as those of alpha,beta-dimethyl-1 ,2,3,4,-tetrahydroisoquinoline-3-carboxylic acid (5 and 6) have been accomplished in high yield and high optical purity. Molecular mechanics calculations on the N-alpha-acetyl and N- methylcarboxamide derivatives of (3R,4R)-6 and (3R,4S)-5 indicate large and moderate energy stabilization for the gauche(-) but not the gauche(+) side-chain conformers of (3R,4S)-5 and (3R,4R)-6, respectively. By symmetry rules, the same holds for (3S,4R)-5 and (3S,4S)-6, respectively. Thus, these amino acids are potential building blocks for the topographical design of peptides (Kazmierski et al., J. Am. Chem. Sec. 1991, 113, 2275-2283) by providing acylated 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid derivatives in which a gauche(-) and not a gauche(+) side-chain conformation is energetically more stable for the L amino acid. Synthetic details and implications of these new amino acids for peptide and protein design are discussed.

  DOI：

  10.1021/jo00086a033
• 作为产物：
  描述：

  (2S,5S,5αS)-1-Benzoyl-2-tert-butyl-3,5-dimethyl-5-(α-methylbenzyl)imidazolidin-4-one 在 盐酸 作用下， 反应 5.0h， 以82%的产率得到(2S,3S)-2,3-dimethylphenylalanine
  参考文献：
  名称：

  New Amino Acids for the Topographical Control of Peptide Conformation: Synthesis of All the Isomers of .alpha.,.beta.-Dimethylphenylalanine and .alpha.,.beta.-Dimethyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic Acid of High Optical Purity

  摘要：

  The synthesis of all four diastereoisomers of alpha,beta-dimethylphenylalanine (4) as well as those of alpha,beta-dimethyl-1 ,2,3,4,-tetrahydroisoquinoline-3-carboxylic acid (5 and 6) have been accomplished in high yield and high optical purity. Molecular mechanics calculations on the N-alpha-acetyl and N- methylcarboxamide derivatives of (3R,4R)-6 and (3R,4S)-5 indicate large and moderate energy stabilization for the gauche(-) but not the gauche(+) side-chain conformers of (3R,4S)-5 and (3R,4R)-6, respectively. By symmetry rules, the same holds for (3S,4R)-5 and (3S,4S)-6, respectively. Thus, these amino acids are potential building blocks for the topographical design of peptides (Kazmierski et al., J. Am. Chem. Sec. 1991, 113, 2275-2283) by providing acylated 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid derivatives in which a gauche(-) and not a gauche(+) side-chain conformation is energetically more stable for the L amino acid. Synthetic details and implications of these new amino acids for peptide and protein design are discussed.

  DOI：

  10.1021/jo00086a033

文献信息

• Asymmetric Synthesis of α,β-Dialkyl-α-phenylalanines via Direct Alkylation of a Chiral Alanine Derivative with Racemic α-Alkylbenzyl Bromides. A Case of High Enantiomer Differentiation at Room Temperature
  作者：Vadim A. Soloshonok、Xuejun Tang、Victor J. Hruby、Luc Van Meervelt

  DOI：10.1021/ol000330o

  日期：2001.2.1

  that the direct alkylation of a Ni(II)-complex of the chiral Schiff base of alanine with (S)-o-[N-(N-benzylprolyl)amino]- benzophenone, with racemic alpha-alkylbenzyl bromides, is a synthetically feasible and methodologically advantageous approach to the target alpha,beta-dialkylphenylalanines over previously reported methods. For the first time we report and rationalize a case of a high enantiomer differentiation

  [图：见正文]这项研究表明，丙氨酸的手性席夫碱的Ni（II）配合物与（S）-o- [N-（N-苄基脯氨酰基）氨基]-二苯甲酮与外消旋体的直接烷基化与先前报道的方法相比，α-烷基苄基溴是对目标α，β-二烷基苯基丙氨酸的合成可行和方法学上有利的方法。我们首次报告并合理化了室温下高对映异构体分化过程的案例。
• Asymmetric Synthesis of (2<i>S</i>,3<i>S</i>)- and (2<i>R</i>,3<i>R</i>)-α,β-Dialkyl-α-amino Acids via Alkylation of Chiral Nickel(II) Complexes of Aliphatic α-Amino Acids with Racemic α-Alkylbenzyl Bromides
  作者：Vadim Soloshonok、Thomas Boettiger、Shawna Bolene

  DOI：10.1055/s-2008-1067172

  日期：2008.8

  This studv has demonstrated that the stereochemical outcome of the direct alkylation of nickel(II) complexes derived from chiral Schiff bases of glycine, alanine, 2-aminobutyric acid, and leucine with racemic α-methylbenzyl bromide depends on the steric bulk of the corresponding amino acid residue. In particular, the alkylation of the alanine complex was found to proceed with a synthetically useful level

  该研究表明，由甘氨酸、丙氨酸、2-氨基丁酸和亮氨酸的手性席夫碱衍生的镍 (II) 配合物与外消旋 α-甲基苄基溴的直接烷基化的立体化学结果取决于相应氨基的空间体积。酸残渣。特别是，发现丙氨酸络合物的烷基化以合成有用水平 (90% de) 的立体选择性进行，提供了对映体纯 (2S,3S)- 或 (2R,3R)-α,β-二甲基苯丙氨酸的简明合成.
• New Amino Acids for the Topographical Control of Peptide Conformation: Synthesis of All the Isomers of .alpha.,.beta.-Dimethylphenylalanine and .alpha.,.beta.-Dimethyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic Acid of High Optical Purity
  作者：Wieslaw M. Kazmierski、Zofia Urbanczyk-Lipkowska、Victor J. Hruby

  DOI：10.1021/jo00086a033

  日期：1994.4

  The synthesis of all four diastereoisomers of alpha,beta-dimethylphenylalanine (4) as well as those of alpha,beta-dimethyl-1 ,2,3,4,-tetrahydroisoquinoline-3-carboxylic acid (5 and 6) have been accomplished in high yield and high optical purity. Molecular mechanics calculations on the N-alpha-acetyl and N- methylcarboxamide derivatives of (3R,4R)-6 and (3R,4S)-5 indicate large and moderate energy stabilization for the gauche(-) but not the gauche(+) side-chain conformers of (3R,4S)-5 and (3R,4R)-6, respectively. By symmetry rules, the same holds for (3S,4R)-5 and (3S,4S)-6, respectively. Thus, these amino acids are potential building blocks for the topographical design of peptides (Kazmierski et al., J. Am. Chem. Sec. 1991, 113, 2275-2283) by providing acylated 1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid derivatives in which a gauche(-) and not a gauche(+) side-chain conformation is energetically more stable for the L amino acid. Synthetic details and implications of these new amino acids for peptide and protein design are discussed.