methyl 6-deoxy-2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose | 263744-58-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 6-deoxy-2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose
• 英文别名: 1-[(3aS,4S,6S,6aR)-4-methoxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-6-yl]ethanone
• CAS: 263744-58-7
• 化学式: C₁₀H₁₆O₅
• 分子量: 216.234
• InChiKey: LZWOIRQYZWWKRX-XGEHTFHBSA-N

物化性质

• 沸点：
  290.1±40.0 °C(predicted)
• 密度：
  1.19±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  methyl 6-deoxy-2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose 在 barium dihydroxide 、 碳酸氢铵 、 溶剂黄146 作用下， 以 乙醇 、 水 为溶剂， 反应 21.25h， 生成 methyl (5S)-5-amino-5-C-carboxy-5,6-dideoxy-α-D-lyxo-hexofuranoside
  参考文献：
  名称：

  与丙氨酸和6-脱氧甘露糖霉素有关的一些糖氨基酸的合成与结构测定

  摘要：

  （5'R）-5'-甲基-5'-[甲基（4S）-2,3-O-异亚丙基-β-L-赤呋喃糖苷-4-C-基]-咪唑啉丁-2'，4'-二酮应用Bucherer-Bergs反应，从甲基6-脱氧-2,3-O-异亚丙基-α-D-lyxo-己呋喃糖苷-5-ulose开始合成。X射线晶体学证实了其5'-R构型。相应的α-氨基酸-甲基（5R）-5-氨基-5-C-羧基-5,6-二脱氧-α-D-lyxo-六呋喃糖苷（替代名称：2- [甲基（4S）-2,3-由上述乙内酰脲通过对异亚丙基的酸水解，然后对乙内酰脲环进行碱性水解，得到O-异亚丙基-β-L-赤呋喃糖苷-4-C-基] -D-丙氨酸。完全脱保护得到5-C-羧基-6-脱氧甘露糖霉素。类似地，甲基（5S）-5-氨基-5-C-羧基-5

  DOI：

  10.1016/s0008-6215(01)00109-4
• 作为产物：
  描述：

  methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside 在 potassium tert-butylate 、 硫酸 作用下， 以 四氢呋喃 为溶剂， 反应 0.42h， 以79%的产率得到methyl 6-deoxy-2,3-O-isopropylidene-α-D-lyxo-hexofuranosid-5-ulose
  参考文献：
  名称：

  Reaction of 5,6-cyclic sulfates derived from glycofuranoses with bases. A one-pot synthesis of 6-deoxy-hexofuranos-5-ulose derivatives

  摘要：

  Methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-alpha-D-mannofuranoside 1 reacted with nitrogen bases to give the corresponding aminosulfates. Strong bases such as sodium tert-butoxide or n-butyllithium afforded methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexanofuranos-5-uloside 7. The reaction was optimized with sodium tert-butoxide and applied to three other 5,6-cyclic sulfates derived from aldofuranosides to give the corresponding keto-aldoses in good yields. (C) 2000 Published by Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)02158-9

文献信息

• Synthesis, Crystal Structure, and Conformation of Methyl 5-Oacetyl-5-cyano-6-deoxy-2,3-O-isopropylidene-β-L-gulofuranoside
  作者：Júlia Mičová、Bohumil Steiner、Miroslav Koóš、Ján Gajdoš、Vratislav Langer、Dalma Gyepesová

  DOI：10.3390/70500437

  日期：——

  Methyl 5-O-acetyl-5-cyano-6-deoxy-2,3-O-isopropylidene-β-L-gulofuranoside was prepared in high yield from methyl 6-deoxy-2,3-O-isopropylidene-α-D-lyxopentodialdo-1,4-furanoside. The configuration at the C5 atom was unambiguosly established by single crystal X-ray analysis of the corresponding 5-O-acetyl derivative. The conformation of the furanose and 1,3-dioxolane rings is also discussed.

  高产率制备了甲基5-O-乙酰基-5-氰基-6-去氧-2,3-O-异亚丙基-β-L-古洛呋喃糖苷，其原料为甲基6-去氧-2,3-O-异亚丙基-α-D-来苏戊二醛-1,4-呋喃糖苷。通过相应5-O-乙酰基衍生物的单晶X射线分析，明确了C5原子的构型。同时，还讨论了呋喃糖和1,3-二恶烷环的构象。
• Some amino sugars structurally related to 6-deoxymannojirimycin precursors prepared from methyl 6-deoxy-2,3-O-isopropylidene-α-d-lyxo-hexofuranosid-5-ulose and methyl 2,3-O-isopropylidene-α-d-lyxo-pentodialdo-1,4-furanoside
  作者：Júlia Mičová、Bohumil Steiner、Miroslav Koóš、Vratislav Langer、Marián Ďurı́k、Dalma Gyepesová、L'ubomı́r Smrčok

  DOI：10.1016/s0008-6215(02)00058-7

  日期：2002.4

  Methyl (5S)-5-C-amino-5-cyano-5-deoxy-2,3-O-isopropylidene-alpha-D-lyxofuranoside has been synthesised from methyl 2,3-O-isopropylidene-alpha-D-lyxo-pentodialdo-1,4-furanoside, applying the Strecker synthesis. Analogously, methyl (5S) and (5R)-5-C-amino-5-cyano-5,6-dideoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosides were prepared from methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose

  甲基（5S）-5-C-氨基-5-氰基-5-脱氧-2,3-O-异亚丙基-α-D-呋喃糖苷已由甲基2,3-O-异亚丙基-α-D-lyxo合成-戊二醛-1,4-呋喃糖苷，应用斯特雷克合成法。类似地，由甲基6-脱氧-甲基制备甲基（5S）和（5R）-5-C-氨基-5-氰基-5,6-二脱氧-2,3-O-异亚丙基-α-D-lyxo-六呋喃糖苷。 2,3-O-异亚丙基-α-D-lyxo-六呋喃糖苷-5-ulose。通过相应的N-乙酰基衍生物的单晶X射线衍射分析明确确定了5-S构型。讨论了五元环的构象。还描述了N-乙酰化氨基腈分别转化为N-乙酰氨基酸乙酯和酰胺的转化。
• A new 6-C-alkylation from an alkyl mannofuranoside 5,6-cyclic sulfate
  作者：Thierry Gourlain、Anne Wadouachi、Daniel Beaupère

  DOI：10.1016/s0008-6215(99)00275-x

  日期：2000.1

  Methyl 6-C-alkyl-6-deoxy-alpha-D-mannofuranoside derivatives have been synthesized from methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-alpha-D-mannofuranoside (1). In a Path A, reaction of the 5,6-cyclic sulfate 1 with 2-lithio-1,3-dithiane afforded 2-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane (2). Treatment of 2 with n-butyllithium then alkyl iodide gave the corresponding 2-(methyl 5-O-alkyl-6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane. Reaction of 2 with n-butyllithium and 5,6-cyclic sulfate 1 furnished 2-[methyl 6-deoxy-2,3-O-isopropylidene-5-O-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-manno-furanosid-6-yl)-alpha-D-mannofuranosid-6-yl]-1,3-dithiane. 2-(Methyl 6-deoxy-2,3-O-isopropylidene-5-O-methyl-alpha-D-mannofuranosid-6-yl)-1,3-dithiane was converted into the lithiated anion, which after treatment with alkyl halide afforded the corresponding 2-alkyl-C-(methyl 6-deoxy-2,3-O-isopropylidene-5-O-methyl-alpha-D-mannofuranosid-6-yl)-1,3-dithiane. In a Path B, 5,6-cyclic sulfate 1 reacted with 2-alkyl-2-lithio-1,3-dithiane derivatives, which led after acidic hydrolysis to 2-alkyl-2-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane accompanied by methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranos-5-uloside as the by-product. This methodology was applied to synthesize 2-(methyl 6-deoxy-2,3-O-isopropylidene-5-O-methyl-alpha-D-mannofuranosid-6-yl)-2-(methyl 6-deoxy-2,3-O-isopropylidene-alpha-D-mannofuranosid-6-yl)-1,3-dithiane. (C) 2000 Elsevier Science Ltd. All rights reserved.