(+)-(S)-2',1':1,2:1",2":3,4-dinaphthcyclohepta-1,3-diene-6-amino-6-carboxylic acid tert-butyl ester | 178065-00-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (+)-(S)-2',1':1,2:1",2":3,4-dinaphthcyclohepta-1,3-diene-6-amino-6-carboxylic acid tert-butyl ester
• 英文别名: Tert-butyl 13-aminopentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene-13-carboxylate
• CAS: 178065-00-4；178065-01-5；201687-37-8
• 化学式: C₂₈H₂₇NO₂
• 分子量: 409.528
• InChiKey: BXZINGYFXMSBCB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  31
• 可旋转键数：
  3
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (+)-(S)-2',1':1,2:1",2":3,4-dinaphthcyclohepta-1,3-diene-6-amino-6-carboxylic acid tert-butyl ester 在 硫酸 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 96.0h， 生成 H-(R)-Bin-OEt
  参考文献：
  名称：

  Novel α,α-disubstituted α-aminoacids with axial dissymmetry and their N- or C-protected derivatives

  摘要：

  Racemic as well as enantiomerically pure 1,1'-binaphthyl-substituted alpha-aminoisobutyric acid (Bin), a new chiral atropoisomeric alpha, alpha-disubstituted glycine, and its biphenyl analogue (Bip), have been prepared with good yields by bis-alkylation of a glycine tert-butyl ester Schiff base with 2,2'-bis(bromomethyl)-1, 1'-binaphthyl and 2,2'-bis(bromomethyl)-1,1'-biphenyl, respectively, under phase transfer conditions. The free aminoacids Bin and Bip, as well as their N-protected (Z, Boc, Fmoc) and/or C-protected (ethyl or tert-butyl esters) derivatives, useful for the incorporation of these new aminoacids into peptides, have been obtained. A slow interconversion between the two enantiomers of the Bip derivatives is generally observed in H-1 NMR at room temperature, with a rotational energy barrier of 59 kJ mol(-1). (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(97)00009-8
• 作为产物：
  描述：

  {[1-(4-chlorophenyl)methylidene]amino}acetic acid tert-butyl ester 在 甲醇 、 氢氧化钾 、 四丁基溴化铵 、 silica gel 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 26.0h， 生成 (+)-(S)-2',1':1,2:1",2":3,4-dinaphthcyclohepta-1,3-diene-6-amino-6-carboxylic acid tert-butyl ester
  参考文献：
  名称：

  Practical resolution of an atropoisomeric α,α-disubstituted glycine with l-phenylalanine cyclohexylamide as chiral auxiliary

  摘要：

  L-Phenylalanine cyclohexylamide has been used as a chiral auxiliary for the medium-scale resolution of 2',1':1,2;1 ",2 ":3,4-dinaphthcyciohepta- 1,3-diene-6-amino-6-carboxylic acid (Bin), an alpha,alpha-disubstituted glycine with only axial dissymmetry. Coupling of X-Bin-OH (X=Ac; Bz) with H-(L)-Phe-NH-C6H11 by the EDC/HOBt method gave the dipeptide diastereoisomers X-(R)-Bin-(L)-Phe-NH-C6H11 and X-(S)-Bin-(L)-Phe-NH-C6H11, which were separated by crystallization (X=Bz) and/or chromatography. Extensive acidic hydrolysis, followed by esterification of the resulting free amino acid enantiomers, led to enantiomerically pure (-)-(R)-H-Bin-OMe and (+)-(S)-H-Bin-OMe with high yields. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00253-5

文献信息

• A Chirally Stable, Atropoisomeric,Cα-Tetrasubstitutedα-Amino Acid: Incorporation into Model Peptides and Conformational Preference
  作者：Fernando Formaggio、Cristina Peggion、Marco Crisma、Claudio Toniolo、Luba Tchertanov、Jean Guilhem、Jean-Paul Mazaleyrat、Yolaine Goubard、Anne Gaucher、Michel Wakselman

  DOI：10.1002/1522-2675(20010228)84:2<481::aid-hlca481>3.0.co;2-c

  日期：2001.2.28

  A variety of model peptides, including four complete homologous series, to the pentamer level, characterized by the recently proposed binaphthyl-based, axially chiral, Cα-tetrasubstituted, cyclic α-amino acid Bin, in combination with Ala, Gly, or Aib residues, was synthesized by solution methods and fully characterized. The solution conformational propensity of these peptides was determined by FT-IR

  多种模型肽，包括四个完整的同源系列，达到五聚体水平，其特征是最近提出的基于联萘的轴向手性 Cα-四取代的环状 α-氨基酸 Bin，与 Ala、Gly 或 Aib 残基组合, 通过溶液法合成并充分表征。这些肽的溶液构象倾向通过FT-IR吸收和1H-NMR技术确定。此外，通过 X 射线衍射在晶体状态下评估了游离氨基酸 (S)-对映异构体和具有异手性序列 -(R)-Bin-Phe- 的 Nα-酰化二肽烷基酰胺的分子结构。综上所述，结果表明含Bin的肽优先采用β-弯头和310个螺旋，尽管在某种程度上，短低聚物在溶液中也会采用完全延伸的构象。我们还证实了 (R)-Bin 将肽链折叠成右手弯曲和螺旋结构的趋势。Bin 残基的绝对构型与 225 nm 附近 1Bb 联萘跃迁的典型强烈激子分裂棉花效应相关。
• A new chiral α-aminoacid with only axial dissymmetry: Synthesis and X-ray analysis of a 1,1′-binaphthyl-substituted α-aminoisobutyric acid (Bin) and of its biphenyl analogue (Bip)
  作者：Jean-Paul Mazaleyrat、Anne Gaucher、Michel Wakselman、Luba Tchertanov、Jean Guilhem

  DOI：10.1016/0040-4039(96)00502-3

  日期：1996.4

  Racemic as well as optically pure 1,1′-binaphthyl-substituted α-aminoisobutyric acid (Bin), a new chiral atropoisomeric α,α-disubstituted glycine, and its biphenyl analogue (Bip), have been prepared by bis-alkylation of a glycine tert-butyl ester Schiff base. The free aminoacids Bin and Bip, as well as their C-and/or N-protected derivatives have been obtained. X-ray analysis of H-Bip-OtBu and H-(S)Bin-OH

  外消旋及光学纯的1,1'-联萘取代的α-氨基异丁酸（Bin），新的手性阻转异构体α，α-二取代的甘氨酸及其联苯类似物（Bip）是通过对a甘氨酸叔丁酯席夫碱。已获得游离氨基酸Bin和Bip以及它们的C和/或N保护的衍生物。提出了H-Bip-OtBu和H-（S）Bin-OH的X射线分析。
• Practical resolution of an atropoisomeric α,α-disubstituted glycine with l-phenylalanine cyclohexylamide as chiral auxiliary
  作者：Jean-Paul Mazaleyrat、Aurelia Boutboul、Yann Lebars、Anne Gaucher、Michel Wakselman

  DOI：10.1016/s0957-4166(98)00253-5

  日期：1998.8

  L-Phenylalanine cyclohexylamide has been used as a chiral auxiliary for the medium-scale resolution of 2',1':1,2;1 ",2 ":3,4-dinaphthcyciohepta- 1,3-diene-6-amino-6-carboxylic acid (Bin), an alpha,alpha-disubstituted glycine with only axial dissymmetry. Coupling of X-Bin-OH (X=Ac; Bz) with H-(L)-Phe-NH-C6H11 by the EDC/HOBt method gave the dipeptide diastereoisomers X-(R)-Bin-(L)-Phe-NH-C6H11 and X-(S)-Bin-(L)-Phe-NH-C6H11, which were separated by crystallization (X=Bz) and/or chromatography. Extensive acidic hydrolysis, followed by esterification of the resulting free amino acid enantiomers, led to enantiomerically pure (-)-(R)-H-Bin-OMe and (+)-(S)-H-Bin-OMe with high yields. (C) 1998 Elsevier Science Ltd. All rights reserved.
• Novel α,α-disubstituted α-aminoacids with axial dissymmetry and their N- or C-protected derivatives
  作者：Jean-Paul Mazaleyrat、Anne Gaucher、Jaroslav Šavrda、Michel Wakselman

  DOI：10.1016/s0957-4166(97)00009-8

  日期：1997.2

  Racemic as well as enantiomerically pure 1,1'-binaphthyl-substituted alpha-aminoisobutyric acid (Bin), a new chiral atropoisomeric alpha, alpha-disubstituted glycine, and its biphenyl analogue (Bip), have been prepared with good yields by bis-alkylation of a glycine tert-butyl ester Schiff base with 2,2'-bis(bromomethyl)-1, 1'-binaphthyl and 2,2'-bis(bromomethyl)-1,1'-biphenyl, respectively, under phase transfer conditions. The free aminoacids Bin and Bip, as well as their N-protected (Z, Boc, Fmoc) and/or C-protected (ethyl or tert-butyl esters) derivatives, useful for the incorporation of these new aminoacids into peptides, have been obtained. A slow interconversion between the two enantiomers of the Bip derivatives is generally observed in H-1 NMR at room temperature, with a rotational energy barrier of 59 kJ mol(-1). (C) 1997 Elsevier Science Ltd.