methyl 6-O-benzyl-2,3-O-isopropylidene-α-D-mannofuranoside | 161365-10-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl 6-O-benzyl-2,3-O-isopropylidene-α-D-mannofuranoside
• 英文别名: (1R)-1-[(3aS,4S,6R,6aS)-4-methoxy-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-6-yl]-2-phenylmethoxyethanol
• CAS: 161365-10-2
• 化学式: C₁₇H₂₄O₆
• 分子量: 324.374
• InChiKey: SEDBMLXDCWEFKI-OWYFMNJBSA-N

物化性质

• 沸点：
  442.5±45.0 °C(predicted)
• 密度：
  1.22±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 6-O-benzyl-2,3-O-isopropylidene-α-D-mannofuranoside 在 盐酸 、 4-二甲氨基吡啶 、 草酰氯 、 偶氮二异丁腈 、 三正丁基氢锡 、 二甲基亚砜 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三乙胺 、 红铝 作用下， 以 二氯甲烷 、 异丙醇 、 甲苯 、 乙腈 为溶剂， 反应 25.0h， 生成 6-O-benzyl-5-deoxy-5-(hydroxyphosphinyl)-α/β-D-mannopyranose
  参考文献：
  名称：

  摘要：

  Starting from methyl 2,3-O-isopropylidene-alpha-D-mannofuranoside (5), methyl 6-O-benzyl-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose (12) was prepared in three steps. The addition reaction of dimethyl phosphonate to 12, followed by deoxygenation of 5-OH group, provided the 5-deoxy-5-dimetltoxyphosphinyl-alpha-D-mannofuranoside derivative 15a and the beta-L-gulofuranoside isomer 15b. Reduction of 15a and 15b with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by the action of HCl and then H2O2, afforded the D-mannopyranose (17) and L-gulopyranose analog 21, each having a phosphinyl group in the hemiacetal ring. These were converted to the corresponding 1,2,3,4,6-penta-O-acetyl-5-methoxyphosphinyl derivatives 19 and 23, respectively, structures and conformations (C-4(1) or C-1(4), resp.) of which were established by H-1-NMR spectroscopy.

  DOI：

  10.1002/1522-2675(200209)85:9<2608::aid-hlca2608>3.0.co;2-f
• 作为产物：
  描述：

  methyl 2,3-O-isopropylidene-α-D-mannofuranoside 在 吡啶 、 sodium hydride 作用下， 以 乙二醇二甲醚 为溶剂， 反应 4.0h， 生成 methyl 6-O-benzyl-2,3-O-isopropylidene-α-D-mannofuranoside
  参考文献：
  名称：

  摘要：

  Starting from methyl 2,3-O-isopropylidene-alpha-D-mannofuranoside (5), methyl 6-O-benzyl-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose (12) was prepared in three steps. The addition reaction of dimethyl phosphonate to 12, followed by deoxygenation of 5-OH group, provided the 5-deoxy-5-dimetltoxyphosphinyl-alpha-D-mannofuranoside derivative 15a and the beta-L-gulofuranoside isomer 15b. Reduction of 15a and 15b with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by the action of HCl and then H2O2, afforded the D-mannopyranose (17) and L-gulopyranose analog 21, each having a phosphinyl group in the hemiacetal ring. These were converted to the corresponding 1,2,3,4,6-penta-O-acetyl-5-methoxyphosphinyl derivatives 19 and 23, respectively, structures and conformations (C-4(1) or C-1(4), resp.) of which were established by H-1-NMR spectroscopy.

  DOI：

  10.1002/1522-2675(200209)85:9<2608::aid-hlca2608>3.0.co;2-f

文献信息

• Elongation of the pentose chain at the terminal carbon atom with Grignard C1 reagents. A study of the homologation reaction
  作者：Halszka Stępowska、Aleksander Zamojski

  DOI：10.1016/s0040-4020(99)00197-0

  日期：1999.4

  with four Grignard C1 reagents: methoxymethyl-, allyloxymethyl-, benzyloxymethyl, and dimethylphenylsilylmethyl-magnesium chlorides. Derivatives of the expected stereoisomeric hexoses were accompanied in some cases by C-4 inverted products. The results have been discussed in terms of α- and β-chelated transition states. It has been found that the RX (X=O,Si) grouping of the Grignard reagent strongly

  使四种立体异构的戊二醛-1,4-呋喃糖酶的衍生物与四种Grignard C 1试剂：甲氧基甲基-，烯丙氧基甲基-，苄氧基甲基和二甲基苯基甲硅烷基甲基-氯化镁反应。预期的立体异构己糖的衍生物在某些情况下还伴有C-4反向产物。已经根据α-和β-螯合的过渡态讨论了结果。已经发现格氏试剂的RX（X = O，Si）分组强烈影响延伸反应的立体化学结果。
• A convenient preparation of 5-benzyl ethers of d-gluco- and d-manno-furanose derivatives
  作者：Halszka Stȩpowska、Aleksander Zamojski

  DOI：10.1016/0008-6215(94)00216-9

  日期：1994.12
• Stereoselectivity in deoxygenation of 5-hydroxy-5-phosphinyl-hexofuranoses (α-hydroxyphosphonates)
  作者：Tadashi Hanaya、Ken-ichi Sugiyama、Heizan Kawamoto、Hiroshi Yamamoto

  DOI：10.1016/s0008-6215(03)00235-0

  日期：2003.7

  The addition of dimethyl phosphonate to six different hexofuranos-5-uloses in the presence of DBU, followed by esterification with methoxalyl chloride and then radical reduction, afforded 5-deoxy-5-dimethoxyphosphinyl-D- and L-hexofuranoses. The stereoselectivity of the deoxygenation and possible transition-state models are discussed. (C) 2003 Elsevier Ltd. All rights reserved.
• ——
  作者：Tadashi Hanaya、Hiroshi Yamamoto

  DOI：10.1002/1522-2675(200209)85:9<2608::aid-hlca2608>3.0.co;2-f

  日期：2002.9

  Starting from methyl 2,3-O-isopropylidene-alpha-D-mannofuranoside (5), methyl 6-O-benzyl-2,3-O-isopropylidene-alpha-D-lyxo-hexofuranosid-5-ulose (12) was prepared in three steps. The addition reaction of dimethyl phosphonate to 12, followed by deoxygenation of 5-OH group, provided the 5-deoxy-5-dimetltoxyphosphinyl-alpha-D-mannofuranoside derivative 15a and the beta-L-gulofuranoside isomer 15b. Reduction of 15a and 15b with sodium dihydrobis(2-methoxyethoxy)aluminate, followed by the action of HCl and then H2O2, afforded the D-mannopyranose (17) and L-gulopyranose analog 21, each having a phosphinyl group in the hemiacetal ring. These were converted to the corresponding 1,2,3,4,6-penta-O-acetyl-5-methoxyphosphinyl derivatives 19 and 23, respectively, structures and conformations (C-4(1) or C-1(4), resp.) of which were established by H-1-NMR spectroscopy.