ethyl (2R,3R,4S,5R)-3-benzyloxy-2-[N-(benzyloxycarbonyl)amino]-4,5-isopropylidenedioxyhexanoate | 186694-57-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (2R,3R,4S,5R)-3-benzyloxy-2-[N-(benzyloxycarbonyl)amino]-4,5-isopropylidenedioxyhexanoate
• 英文别名: ethyl (2R,3R)-3-phenylmethoxy-2-(phenylmethoxycarbonylamino)-3-[(4S,5R)-2,2,5-trimethyl-1,3-dioxolan-4-yl]propanoate
• CAS: 186694-57-5
• 化学式: C₂₆H₃₃NO₇
• 分子量: 471.551
• InChiKey: GQOUMSYNZFZHFE-TWHAJKEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  34
• 可旋转键数：
  12
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  92.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  ethyl (2R,3R,4S,5R)-3-benzyloxy-2-[N-(benzyloxycarbonyl)amino]-4,5-isopropylidenedioxyhexanoate 在 palladium on activated charcoal 咪唑 、 盐酸 、 氢气 、 二异丁基氢化铝 、 三氟乙酸 作用下， 以 四氢呋喃 、 水 、 甲苯 为溶剂， -78.0~20.0 ℃ 、101.33 kPa 条件下， 反应 18.0h， 生成 α-D-fucosamine
  参考文献：
  名称：

  Amino acid based diastereoselective synthesis of fucosamines

  摘要：

  Enantiomerically pure (+)-D-fucosamine 1, (+)-N-methyl-D-fucosamine 2 and (+)-3-O-methyl-D-fucosamine 3 (elsaminose) have been synthesised from known building blocks derived from natural amino acids. Direct and diastereoselective construction of the key intermediate 8 was accomplished by a highly syn,anti-selective aldol reaction between lithiated Schollkopf's bis-lactim ether 7 and the 1,3-dioxolane-4-carboxaldehyde 5. Elaboration of the common intermediate required optional methylation, selective hydrolysis of the bis-lactim ether in the presence of an isopropylidene ketal, lactonization and partial reduction of the carboxylic group. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00376-2
• 作为产物：
  描述：

  (4S,5R)-2,2,5-trimethyl-1,3-dioxolane-4-carbaldehyde 在 盐酸 、 正丁基锂 、 碳酸氢钠 、 sodium carbonate 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 正己烷 、 水 为溶剂， 反应 20.5h， 生成 ethyl (2R,3R,4S,5R)-3-benzyloxy-2-[N-(benzyloxycarbonyl)amino]-4,5-isopropylidenedioxyhexanoate
  参考文献：
  名称：

  Amino acid based diastereoselective synthesis of fucosamines

  摘要：

  Enantiomerically pure (+)-D-fucosamine 1, (+)-N-methyl-D-fucosamine 2 and (+)-3-O-methyl-D-fucosamine 3 (elsaminose) have been synthesised from known building blocks derived from natural amino acids. Direct and diastereoselective construction of the key intermediate 8 was accomplished by a highly syn,anti-selective aldol reaction between lithiated Schollkopf's bis-lactim ether 7 and the 1,3-dioxolane-4-carboxaldehyde 5. Elaboration of the common intermediate required optional methylation, selective hydrolysis of the bis-lactim ether in the presence of an isopropylidene ketal, lactonization and partial reduction of the carboxylic group. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00376-2

文献信息

• Asymmetric Synthesis of D-Fucosamine and <i>N</i>-Methyl-D-Fucosamine
  作者：Vicente Ojea、María Ruiz、José Quintela

  DOI：10.1055/s-1997-696

  日期：——

  (+)-D-fucosamine and (+)-N-methyl-D-fucosamine (the amino sugar moiety of neocarzinostatin) have been synthesized from known building blocks derived from natural amino acids. Direct and diastereoselective construction of the key intermediate 4 was accomplished by a syn-aldol type reaction between Schöllkopf's bislactim ether 2 and the 1,3-dioxolane-4-carboxaldehyde 3. Reduction and monomethylation of a O'Donnell's Schiff base derived from the common amino ester 7 allows an optional access to the N-methyl derivative.

  (+)-D-岩藻糖胺和(+)-N-甲基-D-岩藻糖胺（新卡西诺司他汀的氨基糖分子）是由天然氨基酸衍生的已知结构单元合成的。通过 Schöllkopf 的双内酰胺醚 2 和 1,3-二氧戊环-4-甲醛 3 之间的合成-醛类反应，直接非对映选择性地合成了关键中间体 4。由普通氨基酯 7 衍生出的奥唐纳席夫碱通过还原和单甲基化反应可获得 N-甲基衍生物。