3,4-O-(R)-benzylidene-D-ribono-1,5-lactone | 20603-45-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: 3,4-O-(R)-benzylidene-D-ribono-1,5-lactone
• 英文别名: (2R,3aR,7R,7aS)-7-hydroxy-2-phenyl-3a,4,7,7a-tetrahydro-[1,3]dioxolo[4,5-c]pyran-6-one
• CAS: 20603-45-6
• 化学式: C₁₂H₁₂O₅
• 分子量: 236.224
• InChiKey: XKMPMXJZFPRETR-DNRKLUKYSA-N

物化性质

• 熔点：
  234-236 °C(lit.)
• 沸点：
  471.9±45.0 °C(Predicted)
• 密度：
  1.377±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3,4-O-(R)-benzylidene-D-ribono-1,5-lactone 在 palladium on activated charcoal 吡啶 、 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 silver(l) oxide 、 环己烯 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 151.0h， 生成 (S)-3-p-toluenesulfonyloxy-5-hydroxymethyl-2(5H)-furanone
  参考文献：
  名称：

  3-羟基-2（5 H）-呋喃酮（等渗酸）的同手性或非手性衍生物的合成方法

  摘要：

  根据新方法，基于使用D-核糖内酯作为手性前体或基于2,4-二氧戊烷酸作为合适的非手性前体的环化，合成了几种标题化合物。碱诱导的消除和随后的酸促进的环收缩是从2-O-烷基-3,4-O-亚苄基-D-核糖基-1,5-内酯衍生物制备等渗酸的有效方案。

  DOI：

  10.1016/s0040-4020(01)81841-x
• 作为产物：
  描述：

  卡培他滨杂质25 在 碳酸氢钠 作用下， 以 水 为溶剂， 反应 1.92h， 生成 3,4-O-(R)-benzylidene-D-ribono-1,5-lactone
  参考文献：
  名称：

  Molecular Sieves Mediated Green Per-O-Acetylation of Carbohydrate Templates and Lipase Catalyzed Regioselective Alcoholysis of 2,3,5-Tri-O-Acetyl-D-Ribonolactone

  摘要：

  The per-O-acetylation of D-ribono-1,4-lactone and representative carbohydrates through the combination of acetic anhydride and molecular sieves under solvent-free conditions is demonstrated. The use of 13X/KCl molecular sieves as the heterogeneous catalyst was found to be more efficient than the excess of pyridine normally employed in the conventional method, giving high yields of the expected peracetylated product after 3 h at 25 degrees C or 1 h at 50 degrees C. The transformation can be carried out in gram scale and in an open flask. Additionally, the catalyst is readily separated from the reaction medium and can be reutilized without significant loss of activity. This green procedure for acetylation was extended to D-ribonolactone derivatives and natural carbohydrates. To demonstrate the synthetic utility of the method, 2,3,5-tri-O-acetyl-D-ribonolactone was selected as the substrate for the regioselective alcoholysis of acetyl group catalyzed by Candida antarctica lipase B in EtOH to selectively produce 2,3-di-O-acetyl-D-ribonolactone in gram scale.

  DOI：

  10.5935/0103-5053.20150037

文献信息

• Spectroscopic, crystallographic and computational studies of the formation and isomerization of cyclic acetals and ketals of pentonolactones
  作者：So-Yeop Han、Madeleine M. Joullié、Valery V. Fokin、Nicos A. Petasis

  DOI：10.1016/s0957-4166(00)80400-0

  日期：1994.12

  D-xylonolactone, D-lyxonolactone 2-deoxy-D-ribonolactone toward benzaldehyde and acetone in acidic media, were examined. The reactions involved complex equilibria and were investigated with extensive 13C NMR studies as well as X-ray crystallographic analysis of selected products. Molecular mechanics (MM2) and semiempirical (PM3 and AM1) calculations of some derivatives were carried out in order to facilitate structural

  检查了D-核糖内酯，L-阿拉伯糖内酯，D-木糖内酯，D-苯二酸内酯2-脱氧-D-核糖内酯在酸性介质中对苯甲醛和丙酮的不同反应性。反应涉及复杂的平衡，并通过广泛的13 C NMR研究以及所选产品的X射线晶体学分析进行了研究。为了方便结构和构象的分配，对某些衍生物进行了分子力学（MM2）和半经验（PM3和AM1）计算。D-戊烯-1,4-内酯与苯甲醛和丙酮反应的反应活性差异在结构和构象方面均得到合理化。
• Biosynthesis of porphyrins and related macrocycles. Part 44. Synthetic and stereochemical studies on the proposed spiro intermediate for biosynthesis of the natural porphyrins
  作者：Mark A. Cassidy、Nigel Crockett、Finian J. Leeper、Alan R. Battersby

  DOI：10.1039/p19960002079

  日期：——

  enantiomers of the spiro lactam 4. The enzyme uroporphyrinogen III synthase (cosynthetase), which converts hydroxymethylbilane 1 into uroporphyrinogen III 3, is competitively inhibited more than twenty times more strongly by one enantiomer of 4 than by the other. This finding adds further strong support to the view that cosynthetase acts by generating the spiro pyrrolenine 2 as an intermediate.

  设计了合成螺内酰胺4的两个对映异构体的途径。尿卟啉原III合酶（cosynthetase）将羟甲基胆烷1转化为尿卟啉原III 3，一种对映体4的竞争性抑制作用要强二十倍。其他。这一发现进一步支持了以下观点，即合成酶通过生成螺吡咯烷2作为中间体起作用。
• Clarifying the Use of Benzylidene Protecting Group for D-(+)-Ribono-1,4-Lactone, an Essential Building Block in the Synthesis of C-Nucleosides
  作者：Silvana Casati、Paola Rota、Pietro Allevi、Alessandra Mingione、Roberta Ottria、Pierangela Ciuffreda

  DOI：10.3390/molecules26216447

  日期：——

  have been the subject of renewed interest from the scientific community thanks to their antiviral activity. The COVID-19 global pandemic, indeed, spread light on the antiviral drug Remdesivir, an adenine C-nucleoside analogue. This new attention of the medical community on Remdesivir prompts the medicinal chemists to investigate once again C-nucleosides. One of the essential building blocks to synthetize

  在过去的两年中，核苷类似物是一类成熟的生物活性化合物，由于其抗病毒活性，已成为科学界重新关注的主题。COVID-19 全球大流行确实让人们对抗病毒药物瑞德西韦（一种腺嘌呤C核苷类似物）有所了解。医学界对瑞德西韦的这种新关注促使药物化学家再次研究C-核苷。合成这些化合物的基本组成部分之一是 D-(+)-ribono-1,4-内酯，但与使用不同碳水化合物保护基团相关的一些机制方面仍不清楚。在这里，我们介绍了我们对使用亚苄基作为核糖内酯保护基团的研究，这些保护基团可用于合成C-嘌呤核苷类似物。提供了在不同反应条件下获得的化合物的详细 1D 和 2D NMR 结构研究。此外，使用 CHCl 3和 DMSO的 SM8 溶剂化模型在 B3LYP/6-31G* 理论水平进行分子建模研究，以支持获得的结果。该研究允许澄清机理方面，因为副反应和结构重排喜欢使用亚苄基保护基团。
• Investigations of the formation of cyclic acetal and ketal derivatives of D-ribono-1,4-lactone and 2-deoxy-D-ribono-1,4-lactone
  作者：So-Yeop Han、Madeleine M. Joullié、Nicos A. Petasis、Joaquim Bigorra、Jordi Corbera、Josep Font、Rosa M. Ortuño

  DOI：10.1016/s0040-4020(01)80304-5

  日期：1993.1

  Detailed NMR studies showed that the acetalization of D-ribono-1,4-lactone proceeded with the initial formation of the endo-2,3-acetal derivative, which in the presence of aqueous acids underwent ring expansion and isomerization to the 3,4-acetal of the 1,5-lactone. The endo preference of benzylidene acetals was explained by the transition state conformation of the reactants and the thermodynamic stability

  研究了D-ribono-1,4-内酯和2-deoxy-D-ribono-1,4-内酯与苯甲醛和丙酮在酸性介质中的反应。分离获得的产物并进行表征。在1在极性溶剂中，在300°K和200°K之间检查了D-ribono-1,4-内酯与苯甲醛的热力学控制反应产生的1,5-内酯产物的1 H NMR光谱。在此温度范围内，未观察到1,5-内酯环的构象变化。详细的NMR研究表明，D-ribono-1,4-内酯的缩醛化反应是通过内在的2,3-缩醛衍生物的初步形成而进行的，该衍生物在含水酸的存在下进行扩环并异构化为3,4。 -1，5-内酯的缩醛。通过分子力学计算，反应物的过渡态构象和产物的热力学稳定性解释了亚苄基乙缩醛的内在偏好。
• Benzylidene acetals of the D-ribonolactones: a structural reassessment
  作者：Neil Baggett、J. Grant Buchanan、Moutie Y. Fatah、C. H. Lachut、Kevin J. McCullough、John M. Webber

  DOI：10.1039/c39850001826

  日期：——

  The product of the reaction of D-ribono-1,4-lactone with benzaldehyde and concentrated HCl has been shown, by X-ray crystallography of its acetate, to be 3,4-O-(R)-benzylidene-D-ribono-1,5-lactone and not the 3,5-acetal as previously suggested; with ZnCl2 as catalyst the products are 2,3-O-(R)- and -(S)-benzylidene-D-ribono-1,4-lactone the former preponderating.

  D -ribono-1,4-内酯与苯甲醛和浓盐酸的反应产物，通过其乙酸盐的X-射线晶体学显示为3,4- O-（R）-亚苄基-D- ribono -1,5-内酯，而不是以前建议的3,5-乙缩醛；用ZnCl 2作为催化剂，产物是2，3- O-（R）-和-（S）-亚苄基-D-核糖-1，4-内酯，前者占优势。