3-deoxy-2-C-hydroxymethyl-D-erythro-pentono-1,4-lactone | 20261-94-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3-deoxy-2-C-hydroxymethyl-D-erythro-pentono-1,4-lactone
• 英文别名: α-D-isosaccharino-1,4-lactone；Isosaccharino-1,4-lactone；(3S,5S)-3-hydroxy-3,5-bis(hydroxymethyl)oxolan-2-one
• CAS: 20261-94-3
• 化学式: C₆H₁₀O₅
• 分子量: 162.142
• InChiKey: KMUZIMNQBZNRHZ-NJGYIYPDSA-N

物化性质

• 熔点：
  96 °C
• 沸点：
  354.0±11.0 °C(Predicted)
• 密度：
  1.490±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.3
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  87
• 氢给体数：
  3
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-deoxy-2-C-hydroxymethyl-D-erythro-pentono-1,4-lactone 在 sodium hydroxide 作用下， 生成 α-isosaccharinic acid
  参考文献：
  名称：

  Characterization of α-Isosaccharinic Acid: Lactone and Carboxylic Conformations

  摘要：

  The equilibrium concentrations of alpha-D-isosaccharino-1,4-lactone (ISA(L)) and the carboxylic alpha-D-isosaccharinic acid (HISA) conformations as a function of pH, as well as the rate of the structural rearrangements between the species, have been established in a 0.1 M NaClO4 matrix at 23degreesC using ion chromatographic analytical techniques. The equilibrium constant for the reaction HISA <---->(H+) ISA(L) + H2O was determined to be K-1 = 6.88 +/- 0.64 by curve fitting the experimental equilibrium data. The transformation rate from HISA to ISA(L) exhibits first-order behavior with a half-life of t(1/2) = 122.2 +/- 0.6 min. On the basis of kinetic data, the equilibrium constant was determined to be 6.60 +/- 0.07 with the forward and backward rate constants being k(+) = (4.85 +/- 0.03) x 10(-3) min(-1) and k(-) = (7.35 +/- 0.04) x 10(-4) min(-1), respectively, in agreement with the curve-fitted equilibrium constant. The transformation from ISA(L) to ISA(-) is more rapid and is complete in less than 8 min.

  DOI：

  10.1023/b:josl.0000037771.45926.f2
• 作为产物：
  描述：

  α-isosaccharinic acid 生成 3-deoxy-2-C-hydroxymethyl-D-erythro-pentono-1,4-lactone
  参考文献：
  名称：

  Comprehensive Thermodynamic Model Applicable to Highly Acidic to Basic Conditions for Isosaccharinate Reactions with Ca(II) and Np(IV)

  摘要：

  Isosaccharinate (ISA(-)), a degradation product of cellulose codisposed in low-level nuclear wastes, is expected to be one of the dominant complexing ligands for radionuclides, especially tetravalent actinides. This paper presents a comprehensive thermodynamic model for isosaccharinate reactions with Ca(II) and Np(IV). The model is valid for a wide range of pH values (similar to2-14), ISA(-) concentrations (ranging up to 0.1 m), and ionic strengths (ranging up to 6.54 m), and is based on (1) NMR investigations of HISA(aq) (alpha-D-isosaccharinic acid) and ISL(aq) [dehydration product of HISA(aq)], and the solubility of Ca(ISA)2(c) as a function of pH and concentrations of Ca and ISA(-); (2) NpO2(am) solubility in a wide range of pH values (similar to2-14) and total ISA concentrations of 0.0016 and 0.008 m and at fixed pH values of approximately 5 and 12 with total ISA concentrations ranging from 0.0001 to 0.1 m; and (3) solvent extraction of Np-ISA solutions, containing fixed NaClO4 concentrations ranging from 0.103 to 6.54 m and at fixed pC(H+) values ranging from 1.5 to 1.9, with dibenzoylmethane. Pitzer's ion-interaction approach was used to interpret the data. The different aqueous species required to explain these data included HISA(aq), ISL(aq), Ca(ISA)(+), Np(OH)(3)(ISA)(aq), Np(OH)(3)(ISA)(2)(-), Np(OH)(4)(ISA)(-), and Np(OH)(4)(ISA)(2)(2-). The values of equilibrium constants for reactions involving these species and determined from these data provided close agreements between the observed and predicted concentrations in all of the systems investigated in this study and those reported previously.

  DOI：

  10.1023/b:josl.0000002988.99769.cb

文献信息

• New 2′-<i>C</i>-Branched-Chain Sugar Nucleoside Analogs with Potential Antiviral or Antitumor Activity
  作者：Junior Wolf、Jean-Marc Jarrige、Jean-Claude Florent、David S. Grierson、Claude Monneret

  DOI：10.1055/s-1992-26224

  日期：——

  The synthesis of 2′-C-hydroxymethyl and 2′-C-methyl nucleoside analogs [1-(3-deoxy-2-hydroxymethyl-D-erythro-pentofuranosyl)-thymine (14), the corresponding adenine derivative. 17, 1-(2-methyl-β-D-ribofuranosyl)thymine (20) and 2′-methyladenosine (23)] by coupling of sugar moieties, easily prepared from α-D-isosaccharino-and α-D-glucosaccharino-1,4-lactone derivatives, respectively, with silylated thymine or 6-chloropurine is reported.

  报道了通过将糖基的耦合合成2′-C-羟甲基和2′-C-甲基核苷类似物[1-(3-脱氧-2-羟甲基-D-赤藓糖基)-胸腺嘧啶（14），对应的腺嘌呤衍生物17，1-(2-甲基-β-D-核糖基)胸腺嘧啶（20）和2′-甲基腺苷（23）]，这些糖基分别由α-D-异糖和α-D-葡萄糖-1,4-内酯衍生物轻松制备，并与硅化胸腺嘧啶或6-氯嘌呤耦合而成。
• Chemistry of spectinomycin: its total synthesis, stereocontrolled rearrangement, and analogs
  作者：Stephen Hanessian、René Roy

  DOI：10.1139/v85-026

  日期：1985.1.1

  The total stereocontrolled synthesis of the antibiotic spectinomycin is described, based on the regiospecific functionalization and manipulation of appropriate starting materials. The tertiary keto...

  基于区域特异性功能化和适当起始材料的操作，描述了抗生素壮观霉素的总立体控制合成。三级酮...
• A robust method for the synthesis and isolation of β-gluco-isosaccharinic acid ((2R,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid) from cellulose and measurement of its aqueous pKa
  作者：Paul B. Shaw、Glenn F. Robinson、Craig R. Rice、Paul N. Humphreys、Andrew P. Laws

  DOI：10.1016/j.carres.2011.11.022

  日期：2012.2

  but effective method for the synthesis of a mixture containing equal portions of the two isosaccharinic acids ((2S,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid and (2R,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid) and the separation of the two as their tribenzoate esters. We also report for the first time the aqueous pK(a) of beta-(gluco)isosaccharinic acid (3.61).

  在碱性制浆中，木浆在高温下与浓碱水溶液反应。除了生产用于造纸的纤维素外，碱性制浆还产生大量的异糖醛酸作为废品。异糖精酸是潜在有用的原料：它们是良好的金属螯合剂，并且以其对映体纯的形式，它们是有价值的碳骨架，具有预定的立体化学，可以轻松地功能化以用于合成。尽管如此，尚没有用于分离纯β-（葡萄糖）异糖精酸的简单方法，并且已经进行了非常有限的工作来确定该化合物的化学和物理性质。我们在这里报告了一种非常简单但有效的方法，用于合成包含相等比例的两种异糖苷酸（（2S，4S）-2,4,5-三羟基-2-（羟甲基）戊酸和（2R，4S ）-2,4,5-三羟基-2-（羟甲基）戊酸）和两者的分离为其三苯甲酸酯。我们还首次报告了β-（葡萄糖）异糖精酸（3.61）的水性pK（a）。
• Developing cellulosic waste products as platform chemicals: protecting group chemistry of α-glucoisosaccharinic acid
  作者：Michael Almond、Mustapha G. Suleiman、Matthew Hawkins、Daniel Winder、Thomas Robshaw、Megan Waddoups、Paul N. Humphreys、Andrew P. Laws

  DOI：10.1016/j.carres.2017.11.013

  日期：2018.1

  beta-glucoisosaccharinic acids ((2S,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid and (2R,4S)-2,4,5-trihydroxy-2-(hydroxymethyl)pentanoic acid) which are produced when cellulosic materials are treated with aqueous alkali are potentially valuable platform chemicals. Their highly functionalised carbon skeleton, with fixed chirality at C-2 and C-4, makes them ideal starting materials for use in synthesis. In order

  α和β-葡萄糖异糖酸（（2S，4S）-2,4,5-三羟基-2-（羟甲基）戊酸和（2R，4S）-2,4,5-三羟基-2-（羟甲基）戊酸纤维素材料用碱水溶液处理时产生的）可能是有价值的平台化学品。它们具有高度官能化的碳骨架，在C-2和C-4上具有固定的手性，使其成为用于合成的理想起始原料。为了评估这些糖精酸作为平台化学品的潜力，我们探索了内酯形式的α-葡萄糖异糖精酸（α-GISAL）的保护基化学。我们在这里报告了单步和多步反应途径的使用，可导致α-GISAL的三个不同羟基的区域选择性保护。我们报告了单独或成对保护三个不同羟基的策略。我们还报告了一系列三-O-保护的α-GISAL衍生物的合成，其中许多产品都包含正交保护基。
• Synthesis of Enantiomerically Pure Heterocycles: Access to Hydroxylated Piperidines from a Sugar Lactone
  作者：Christine Thomassigny、Khalil Bennis、Jacques Gelas

  DOI：10.1055/s-1997-1167

  日期：1997.2

  A protected hydroxylated piperidine 7 and its bicyclo- and substituted diastereoisomers 12 and 13, respectively, have been synthesizes from α-D-isosaccharino-1,4-lactone (3), in two very short sequences.

  受保护的羟基化哌啶 7 及其双环和取代的非对映异构体 12 和 13 分别由 α-D-异糖精-1,4-内酯 (3) 以两个非常短的序列合成。