methyl 2,3-O-isopropylidene-6-O-p-toluenesulfonyl-α-D-mannofuranoside | 40789-24-0

• 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 2,3-O-isopropylidene-6-O-p-toluenesulfonyl-α-D-mannofuranoside
• CAS: 40789-24-0
• 化学式: C₁₇H₂₄O₈S
• 分子量: 388.439
• InChiKey: SQBDAVFKGPUMQW-OWYFMNJBSA-N

物化性质

• 沸点：
  531.6±50.0 °C(Predicted)
• 密度：
  1.37±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.95
• 重原子数：
  26.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  100.52
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  methyl 2,3-O-isopropylidene-6-O-p-toluenesulfonyl-α-D-mannofuranoside 在 镍 氢气 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 pyridinium chlorochromate 作用下， 以 乙二醇二甲醚 、 乙醇 、 二氯甲烷 为溶剂， -40.0~20.0 ℃ 、101.33 kPa 条件下， 反应 8.0h， 生成 methyl 5,6-dideoxy-2,3-O-isopropylidene-5-dimethoxyphosphinyl-β-L-gulofuranoside
  参考文献：
  名称：

  制备 5,6-Dideoxy-5-dimethylphosphinyl-D-和-L-hexofuranoses 的立体选择性，以及 5,6-Dideoxy-5-hydroxyphosphinyl-L-galactopyranose（P-in-the-Ring）的有效合成L-岩藻糖类似物）

  摘要：

  将膦酸二甲酯添加到 5 种 6-O-tosyl-hexofuranos-5-uloses 3a-e（α-D-xylo、α-D-ribo、β-D-arabino、α-D-lyxo 和 β -D-ribo) 在 DBU 存在下，然后在 Raney-Ni (W-4) 存在下催化氢解，得到 (5S)- 和 (5R)-5,6- 二脱氧-己呋喃糖衍生物1:0-2:1，取决于中间体5,6-二脱氧-己-5-烯呋喃糖的呋喃糖环的β-侧上的取代基种类。由 3-O-benzyl-5,6-dideoxy-1,2- 有效地制备了 L-岩藻糖类型的 P-in-the-ring 糖类似物 5,6-dideoxy-5-hydroxyphosphinyl-L-galactopyranoses O-异亚丙基-5-二甲氧基膦基-α-L-呋喃半乳糖很容易通过上述选择性制备得到。

  DOI：

  10.1246/bcsj.66.2315
• 作为产物：
  描述：

  4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-6-methoxy-2,2-dimethyltetrahydrofuro[3,4-d][1,3]dioxole 在 吡啶 、 溶剂黄146 作用下， 反应 12.75h， 生成 methyl 2,3-O-isopropylidene-6-O-p-toluenesulfonyl-α-D-mannofuranoside
  参考文献：
  名称：

  制备 5,6-Dideoxy-5-dimethylphosphinyl-D-和-L-hexofuranoses 的立体选择性，以及 5,6-Dideoxy-5-hydroxyphosphinyl-L-galactopyranose（P-in-the-Ring）的有效合成L-岩藻糖类似物）

  摘要：

  将膦酸二甲酯添加到 5 种 6-O-tosyl-hexofuranos-5-uloses 3a-e（α-D-xylo、α-D-ribo、β-D-arabino、α-D-lyxo 和 β -D-ribo) 在 DBU 存在下，然后在 Raney-Ni (W-4) 存在下催化氢解，得到 (5S)- 和 (5R)-5,6- 二脱氧-己呋喃糖衍生物1:0-2:1，取决于中间体5,6-二脱氧-己-5-烯呋喃糖的呋喃糖环的β-侧上的取代基种类。由 3-O-benzyl-5,6-dideoxy-1,2- 有效地制备了 L-岩藻糖类型的 P-in-the-ring 糖类似物 5,6-dideoxy-5-hydroxyphosphinyl-L-galactopyranoses O-异亚丙基-5-二甲氧基膦基-α-L-呋喃半乳糖很容易通过上述选择性制备得到。

  DOI：

  10.1246/bcsj.66.2315

文献信息

• Highly functionalized glyco-conjugated hexahydroazepindiones from saccharide imides via the Norrish type II reaction
  作者：Markus Stark、Joachim Thiem

  DOI：10.1016/j.carres.2006.03.016

  日期：2006.7

  Starting from readily available protected 6-tosylates of D-glucose and D-mannose in both their pyranoside and furanoside forms as well as 6-tosylates of alpha-D-galactopyranose, the corresponding primary succinimido derivatives were obtained in good yield by nucleophilic displacement with potassium succinimide. These imido sugars were photochemically transformed into hexahydroazepindione derivatives such

  从易于获得的吡喃糖苷和呋喃糖苷形式的D-葡萄糖和D-甘露糖保护的6-甲苯磺酸盐以及α-D-吡喃半乳糖的6-甲苯磺酸盐开始，通过亲核置换并琥珀酰亚胺钾。例如通过Norrish II型反应，将这些亚氨基糖光化学转化为六氢a庚啶二酮衍生物。如所期望的，分子内烷基化通过1，6 H-吸收进行，导致稳定的双基。光反应的区域化学受构型，构象和电子特征的控制，有时受保护基团的影响。使用该途径，开发了一种新型的高度官能化的糖衍生的杂环的简便方法。
• Inversion of regioselectivity in reactions of diols through the use of hexamethylenestannylene acetals as intermediates
  作者：T.Bruce Grindley、Xianqi Kong

  DOI：10.1016/s0040-4039(00)73960-8

  日期：1993.8

  Hexamethylenestannylene acetals obtained from a variety of carbohydrate-derived terminal 1,2-diols give good to excellent regioselectivity for tosylation at the secondary oxygen. In contrast, non-cyclic dialkylstannylene acetals react mainly at the primary oxygen. These results are attributed to the greater stability of the dominant stannylene acetal dimers for hexamethylenestannylene acetals.
• Kong, Xianqi; Grindley, T. Bruce, Canadian Journal of Chemistry, 1994, vol. 72, # 12, p. 2396 - 2404
  作者：Kong, Xianqi、Grindley, T. Bruce

  DOI：——

  日期：——
• The chemoenzymatic synthesis of 9-substituted 3,9-dideoxy-d-glycero-d-galacto-2-nonulosonic acids
  作者：David C.M. Kong、Mark von Itzstein

  DOI：10.1016/s0008-6215(97)10014-3

  日期：1997.12

  A series of C-6 functionalised mannosides has been synthesised. Subsequent exposure of 6-azido-6-deoxy-D-mannopyranose and 6-bromo-6-deoxy-D-mannopyranose to Neu5Ac aldolase and sodium pyruvate provided the corresponding 9-azido- and 9-bromo-3,9-dideoxy-D-glycero-D-galacto-2-nonulosonic acid, respectively. (C) 1998 Elsevier Science Ltd.
• ——
  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.