2,4-anhydro-3,5-di-O-benzyl-D-lyxonic acid | 146820-75-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,4-anhydro-3,5-di-O-benzyl-D-lyxonic acid
• 英文别名: (2S,3S,4R)-3-phenylmethoxy-4-(phenylmethoxymethyl)oxetane-2-carboxylic acid
• CAS: 146820-75-9
• 化学式: C₁₉H₂₀O₅
• 分子量: 328.365
• InChiKey: LKFICGVLDQZQKM-SQNIBIBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  24
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  3,5-di-O-benzyl-D-xylono-γ-lactone 在 吡啶 、 lithium hydroxide 、 potassium carbonate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.67h， 生成 2,4-anhydro-3,5-di-O-benzyl-D-lyxonic acid
  参考文献：
  名称：

  Oxetane δ‐Amino Acids: Chemoenzymatic Synthesis of 2,4‐Anhydro‐5‐N‐(t‐butoxycarbonyl)amino‐D‐lyxonic Acid

  摘要：

  Starting from 1,2-O-isopropylidene-D-xylose, methyl 2,4-anhydro-3,5-di-O-benzyl-D-lyxonate ( 4) was synthesized. Debenzylation and transformation of the primary hydroxyl group yielded methyl 2,4-anhydro-5-N-(t-butoxycarbonyl)amino-D-lyxonate (9). While transesterification of 4 under basic reaction conditions was straightforward, an analogous reaction with 9 was not successful. After screening of several lipases, the enzymatic transesterification of 9 was achieved with lipase L2 from Candida antarctica to furnish the title compound 2,4-anhydro-5-N-(t-butoxycarbonyl)amino-D-lyxonic acid in excellent yield. The stereochemistry at the oxetane ring was proven by an x-ray structure of the intermediate methyl 2,4-anhydro-5-azido-D-lyxonate.[GRAPHICS]

  DOI：

  10.1080/07328300600732485

文献信息

• Ring contraction reactions of 2-O-methanesulfonates of α-hydroxy-γ-lactones in aqueous medium to oxetane-2-carboxylic acids: A convenient synthesis of 3′-O-methyloxetanocin and a formal synthesis of oxetanocin
  作者：Anil K. Saksena、Ashit K. Ganguly、Viyyoor M. Girijavallabhan、Russell E. Pike、Yao-Tsung Chen、Mohindar S. Puar

  DOI：10.1016/0040-4039(93)88027-g

  日期：1992.12

  thiohydroxamic ester 17 directly provided the key oxetanosyl-thiopyridyl glycosides 18 which were successfully coupled to N-benzoyladenine. A two-step ring contraction of the tosylate 7 to the oxetane-2-carboxamide 23 is described. Attempted ring contraction of the triflate 24 gave the unexpected products 25 and 26. A ring expansion reaction (e.g. 14a → 21a) was also observed.

  硫代异羟肟酸酯17的Barton脱羧重排15直接提供了关键的氧杂环糖基-硫代吡啶基糖苷18，它们成功地与N-苯甲酰腺嘌呤偶联。描述了甲苯磺酸酯7到氧杂环丁烷-2-羧酰胺23的两步环收缩。尝试的三氟甲磺酸酯24的环收缩产生了意想不到的产物25和26。还观察到环膨胀反应（例如14a → 21a）。