methyl 3-azido-3,4-dideoxy-4-C-methylene-α-L-threo-pentopyranoside | 74857-68-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: methyl 3-azido-3,4-dideoxy-4-C-methylene-α-L-threo-pentopyranoside
• 英文别名: (2R,3R,4S)-4-azido-2-methoxy-5-methylideneoxan-3-ol
• CAS: 74857-68-4
• 化学式: C₇H₁₁N₃O₃
• 分子量: 185.183
• InChiKey: RBILFCCJCUMUOU-RRKCRQDMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.59
• 重原子数：
  13.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  87.45
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  methyl 3-azido-3,4-dideoxy-4-C-methylene-α-L-threo-pentopyranoside 生成 methyl 4-C-azidomethyl-3,4-dideoxy-β-D-glycero-pent-3-enopyranoside
  参考文献：
  名称：

  A novel synthesis of methyl .alpha.-L-garosaminide which illustrates a stereocontrolled approach to the cis-hydroxyamino moiety of amino sugars

  摘要：

  DOI：

  10.1021/ja00531a050
• 作为产物：
  描述：

  methyl 2,3-anhydro-4-C-methylene-β-D-erythro-pentopyranoside 生成 methyl 3-azido-3,4-dideoxy-4-C-methylene-α-L-threo-pentopyranoside
  参考文献：
  名称：

  A novel synthesis of methyl .alpha.-L-garosaminide which illustrates a stereocontrolled approach to the cis-hydroxyamino moiety of amino sugars

  摘要：

  DOI：

  10.1021/ja00531a050

文献信息

• Stereocontrolled routes to <i>cis</i>-hydroxyamino sugars. Part VI. A synthesis of garosamine
  作者：Henry W. Pauls、Bert Fraser-Reid

  DOI：10.1139/v84-261

  日期：1984.8.1

  The exocyclic olefin, 5, obtained from the known epoxy uloside, methyl 2,3-anhydro-β-D-erythro-pentopyranosid-4-ulose, 3, reacts with ammonia or methylamine to give the 3-amino-3-deoxy or 3-methylamino-3-deoxy derivatives respectively. The benzamide, 8c, obtained from the former, reacts with iodonium ion to give an oxazoline in which the cis relationship between the tertiary alcohol and the 3-amino group of garosamine is secured. Deiodination is followed by a one-pot N-methylation and reduction. A hydrolysis gives methyl α-L-garosamimide 2. In a second route, the urethane, 16c, reacts with iodonium ion to give an oxazolidone 17a. This reaction establishes the N-hydroxyamino moiety and circumvents the N-methylation/reduction steps. Deiodination followed by deprotection yields methyl α-L-garosaminide 2. Both routes require eight steps from 3 with overall yields of 14% and 11%, respectively.

  从已知的环氧乌洛糖苷，甲基2,3-脱水-β-D-赤脂-戊聚糖-4-乌洛糖获得的外环烯烃5，分别与氨或甲胺反应，得到3-氨基-3-脱氧或3-甲基氨基-3-脱氧衍生物。从前者获得的苯甲酰胺8c，与碘离子反应，形成一种噁唑啉，其中保证了三级醇和加罗沙胺的3-氨基团之间的顺式关系。脱碘后进行一锅式N-甲基化和还原。水解得到甲基α-L-加罗沙胺酰胺2。在第二条路线中，尿素酯16c与碘离子反应，形成一种噁唑酮17a。该反应建立了N-羟基氨基团，避开了N-甲基化/还原步骤。脱碘后去保护得到甲基α-L-加罗沙胺苷2。这两种途径从3经过八个步骤，总产率分别为14%和11%。