(3R)-3-<<(3'R)-3'-hydroxybutanoyl>oxy>butanoic acid tert-butyl ester | 116761-28-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: (3R)-3-<<(3'R)-3'-hydroxybutanoyl>oxy>butanoic acid tert-butyl ester
• 英文别名: (3R)-3-[((3'R)-3'-hydroxybutyryl)oxy]butyric acid (tert-butyl)ester；[(2R)-4-[(2-methylpropan-2-yl)oxy]-4-oxobutan-2-yl] (3R)-3-hydroxybutanoate
• CAS: 116761-28-5
• 化学式: C₁₂H₂₂O₅
• 分子量: 246.304
• InChiKey: QLXTYEAOSUPHQK-RKDXNWHRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R)-3-<<(3'R)-3'-hydroxybutanoyl>oxy>butanoic acid tert-butyl ester 在 吡啶 、 草酰氯 、 三氟乙酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 生成 (R,R,R,R,R,R,R,S)-α-benzyl-ω-hydroxyoctakis
  参考文献：
  名称：

  Synthesis and Structure of Linear and Cyclic Oligomers of 3-Hydroxybutanoic Acid with Specific Sequences of (R)- and (S)-Configurations

  摘要：

  To study the stereoselectivity of enzymatic cleavage of poly(3-hydroxybutyrates) (PHB) in a well-defined system (purified depolymerase and monodisperse substrate of specific relative configuration), linear and cyclic oligomers of HE (OHBs) containing (R)- and (S)-3-hydroxybutanoate residues were synthesized. The starting material (R)-HB was prepared from natural sPHB, and (S)-HB by enantioselective reduction of 3-oxobutanoate: with yeast or with H-2/Noyori-Taber catalyst (Scheme 2). The HE building blocks were then protected (O-benzyl/tert-butyl ester; Scheme 3) and coupled to give dimers 3, 4 tetramers 5-9, and octamers 10-18; for analytical comparison, a 3mer, 5mer, 6mer, and 7mer (19-22) were also prepared. Two of the tetramers were subjected to macrolactonization conditions (Yamaguchi) to give the cyclic tetramers 23 and 25 and octamers 24 and 26. All new compounds were fully characterized (m.p., [alpha](D), CD, IR, H-1- and C-13-NMR, MS, elemental analysis). Single-crystal X-ray structure analyses were performed with oligolides 24 and 25 ( Figs. 2 and 4), and the structures, as well as the crystal packing, were compared with those of analogs containing only (R)-HB units or consisting of 3-amino- instead of 3-hydroxybutanoic-acid moieties.

  DOI：

  10.1002/(sici)1522-2675(19981216)81:12<2430::aid-hlca2430>3.0.co;2-w
• 作为产物：
  描述：

  (R)-3-(benzyloxy)butanoic acid tert-butyl ester 在 palladium on activated charcoal 吡啶 、 氢气 、 溶剂黄146 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 35.0h， 生成 (3R)-3-<<(3'R)-3'-hydroxybutanoyl>oxy>butanoic acid tert-butyl ester
  参考文献：
  名称：

  Cyclische Oligomere von（R）-3-Hydroxybuttersäure：Herstellung和strukturelle Aspekte †

  摘要：

  （R）-3-羟基丁酸的环状低聚物：制备和结构方面。

  DOI：

  10.1002/hlca.19930760518

文献信息

• High-Yield Synthesis of 20-, 24-, and 28-Membered Macropentolide, -hexolide, and -heptolide, Respectively, from (<i>R</i>)- or (<i>S</i>)-3-hydroxybutanoic acid under<i>Yamaguchi</i>'s macrolactonization conditions
  作者：Dieter Seebach、Urs Brändli、Peter Schnurrenberger、Michael Przybylski

  DOI：10.1002/hlca.19880710119

  日期：1988.2.3

  oligomers formed in ca. 50% yield from enantiomerically pure 3-hydroxybutanoic acid under Yamaguchi's macrolactonization conditions. The FAB mass spectra of the MH+, M Na+, and MCs+ are reported (Figs. 2, 3, 5, and 6). No cyclic tetramer is detected. The 1H-NMR spectra of the cyclic oligomers, of the monomer, and of the polymer (PHB) are very similar (Fig. 4). Directed synthesis of the open-chain dimer and

  大环戊内酯1，己内酯2和庚内酯3构成ca。形成在所述低聚物的80％约 在山口的大环内酯化条件下，对映体纯的3-羟基丁酸的收率为50％。报道了M H +，M Na +和M Cs +的FAB质谱图（图2、3、5和6）。未检测到环状四聚体。环状低聚物，单体和聚合物（PHB）的1 H-NMR谱图非常相似（图4）。3-羟基丁酸的开链二聚体和四聚体的直接合成和尝试的环化作用不会导致环状四聚体的分离。
• Synthesis of Oligo(3-hydroxybutanoate)(OHB)-Containing Peptides with High Binding Affinity to a Class-I-MHC Protein
  作者：Dieter Seebach、Sorana Poenaru、Gerd Folkers、Didier Rognan

  DOI：10.1002/hlca.19980810529

  日期：——

  have now synthesized the first conjugates (1–4) of oligopeptides with oligo[(R)-3-hydroxybutanoates] (OHB) as analogs of MHC-binding peptides. Of the approaches chosen (Scheme 1), a fragment coupling of a hydroxy-butanoyl-amido ester (17 and 19) with an [(aminoalkanoyl)oxy]butanoyl chloride (27; Scheme 3), followed by two peptide-coupling steps (Scheme 4), turned out to be most efficient. The conjugates

  在免疫系统的中心，有主要的组织相容性（MHC）蛋白/九肽复合物，可被T细胞识别。九肽由三个区域组成：一个N末端的区域包含三个氨基酸残基，在第2位具有一个精氨酸;一个C末端的区域具有9个赖氨酸或精氨酸;一个中心可变的五个残基之一（参见图1）。现在，我们已经合成的第一缀合物（1 - 4）寡肽用寡[（[R）-3- hydroxybutanoates]（OHB）作为MHC结合肽的类似物。在选择的方法中（方案1），是羟基丁酸酰氨基酯的片段偶联（17和19）用[（氨基烷酰基）氧基]丁酰氯（27；方案3），然后进行两个肽偶联步骤（方案4），被证明是最有效的。H-Gln-Arg-Leu-（HB）3,4 -Lys-OH（1和2）和H-Ala-Arg-Leu-（HB）3,4 -Lys-OH（3和4）的共轭物是由此获得纯净的形式。具有N端谷氨酰胺的共轭物1和2具有形成焦谷氨酸残基的趋势（见图2）。）。在不同温度
• Nonapeptide Analogues Containing (<i>R</i>)-3-Hydroxybutanoate and β-Homoalanine Oligomers:  Synthesis and Binding Affinity to a Class I Major Histocompatibility Complex Protein
  作者：Sorana Poenaru、José R. Lamas、Gerd Folkers、José A. López de Castro、Dieter Seebach、Didier Rognan

  DOI：10.1021/jm981123l

  日期：1999.7.1

  Crystal structures of antigenic peptides bound to class I MHC proteins suggest that chemical modifications of the central part of the bound peptide should not alter binding affinity to the MHC restriction protein but could perturb the T-cell response to the parent epitope. In our effort in designing nonpeptidic high-affinity ligands for class I MHC proteins, oligomers of (R)-3-hydroxybutanoate and(or) beta-homoalanine have been substituted for the central part of a HLA-B27-restricted T-cell epitope of viral origin. The affinity of six modified peptides to the B*2705 allele was determined by an in vitro stabilization assay. Four out of the six designed analogues presented an affinity similar to that of the parent peptide. Two compounds, sharing the same stereochemistry (R,R,S,S) at the four stereogenic centers of the nonpeptidic spacer, bound to B*2705 with a 5-6-fold decreased affinity. Although the chiral spacers do not strongly interact with the protein active site, there are configurations which are not accepted by the MHC binding groove, probably because of improper orientation of some lateral substituents in the bound state and different conformational behavior in the free state, However we demonstrate that beta-amino acids can be incorporated in the sequence of viral T-cell epitopes without impairing MHC binding. The presented structure-activity relationships open the door to the rational design of peptide-based vaccines and of nonnatural T-cell receptor antagonists aimed at blocking peptide-specific T-cell responses in MHC-associated autoimmune diseases.
• SEEBACH, DIETER;BRANDLI, URS;SCHNURRENBERGER, PETER;PRZYBYLSKI, MICHAEL, HELV. CHIM. ACTA, 71,(1988) N 1, 155-167
  作者：SEEBACH, DIETER、BRANDLI, URS、SCHNURRENBERGER, PETER、PRZYBYLSKI, MICHAEL

  DOI：——

  日期：——