ethyl 2,3-di-O-benzyl-1-thio-α-D-mannopyranoside | 152964-72-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,3-di-O-benzyl-1-thio-α-D-mannopyranoside
• 英文别名: (2R,3R,4S,5S,6R)-6-ethylsulfanyl-2-(hydroxymethyl)-4,5-bis(phenylmethoxy)oxan-3-ol
• CAS: 152964-72-2
• 化学式: C₂₂H₂₈O₅S
• 分子量: 404.527
• InChiKey: YQEXYJAVAOYYBS-LXHROKJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  93.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 2,3-di-O-benzyl-1-thio-α-D-mannopyranoside 在 三氟化硼乙醚 、 三甲基铝 作用下， 以 正己烷 、 甲苯 、 乙腈 为溶剂， 反应 10.0h， 生成 S-ethyl 2,3-di-O-benzyl-4,6-O-[α-2-(2-iodophenyl)ethylthiocarbonyl]ethylidene-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  4,6-O-[1-Cyano-2-(2-iodophenyl)ethylidene] Acetals. Improved Second-Generation Acetals for the Stereoselective Formation of β-d-Mannopyranosides and Regioselective Reductive Radical Fragmentation to β-d-Rhamnopyranosides. Scope and Limitations

  摘要：

  The [1-cyano-2-(2-iodophenyl)]ethylidene group is introduced as an acetal-protecting group for carbohydrate thioglycoside donors. The group is easily introduced under mild conditions, over short reaction times, and in the presence of a wide variety of other protecting groups by the reaction of the 4,6-diol with triethyl (2-iodophenyl)orthoacetate and camphorsulfonic acid, followed by trimethylsilyl cyanide and boron trifluoride etherate. The new protecting group conveys strong beta-selectivity with thiomannoside donors and undergoes a tin-mediated radical fragmentation to provide high yields of the synthetically challenging beta-rhamnopyranosides. The method is also applicable to the glucopyranosides when high beta-selectivity is observed in the coupling reaction and alpha-quinovosides are formed selectively in the radical fragmentation step. In the galactopyranoside series, beta-glycosides are formed selectively on coupling to donors protected by the new system, but the radical fragmentation is unselective and gives mixtures of the 4- and 6-deoxy products. Variable-temperature NMR studies for the glycosylation step, which helped define an optimal protocol, are described.

  DOI：

  10.1021/jo0526688
• 作为产物：
  描述：

  ethyl 2,3-di-O-benzyl-4,6-O-benzylidene-1-thio-α-D-mannopyranoside 在 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 以89 %的产率得到ethyl 2,3-di-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  β-1,4-甘露糖醛酸的光敏氟标签辅助收敛合成

  摘要：

  通过化学方法快速合成糖类是满足明确聚糖探测其生物学功能需求的有效途径。在此，通过在糖苷的端基异构位置引入光敏氟标签，建立了一种可行且方便的糖类合成策略。该标签不仅可用于聚四氟乙烯辅助的快速纯化，还可作为碳水化合物还原端的临时保护基团。通过光解对标签进行正交脱保护后，标签保护的糖苷可以转化为新的糖基供体，用于聚合合成。通过结合 β-导向 C-5 羧酸盐糖基化策略，有效地制备了 β-1,4-甘露糖醛酸。

  DOI：

  10.1021/acs.orglett.3c01179

文献信息

• Garegg, Per J.; Kvarnstroem, Ingemar; Niklasson, Annika, Journal of Carbohydrate Chemistry, 1993, vol. 12, # 7, p. 933 - 954
  作者：Garegg, Per J.、Kvarnstroem, Ingemar、Niklasson, Annika、Niklasson, Gunilla、Svensson, Stefan C. T.

  DOI：——

  日期：——
• 4,6-<i>O</i>-[1-Cyano-2-(2-iodophenyl)ethylidene] Acetals. Improved Second-Generation Acetals for the Stereoselective Formation of β-<scp>d</scp>-Mannopyranosides and Regioselective Reductive Radical Fragmentation to β-<scp>d</scp>-Rhamnopyranosides. Scope and Limitations
  作者：David Crich、Albert A. Bowers

  DOI：10.1021/jo0526688

  日期：2006.4.1

  The [1-cyano-2-(2-iodophenyl)]ethylidene group is introduced as an acetal-protecting group for carbohydrate thioglycoside donors. The group is easily introduced under mild conditions, over short reaction times, and in the presence of a wide variety of other protecting groups by the reaction of the 4,6-diol with triethyl (2-iodophenyl)orthoacetate and camphorsulfonic acid, followed by trimethylsilyl cyanide and boron trifluoride etherate. The new protecting group conveys strong beta-selectivity with thiomannoside donors and undergoes a tin-mediated radical fragmentation to provide high yields of the synthetically challenging beta-rhamnopyranosides. The method is also applicable to the glucopyranosides when high beta-selectivity is observed in the coupling reaction and alpha-quinovosides are formed selectively in the radical fragmentation step. In the galactopyranoside series, beta-glycosides are formed selectively on coupling to donors protected by the new system, but the radical fragmentation is unselective and gives mixtures of the 4- and 6-deoxy products. Variable-temperature NMR studies for the glycosylation step, which helped define an optimal protocol, are described.
• Photosensitive Fluorous Tag-Assisted Convergent Synthesis of β-1,4-Mannuronates
  作者：Yingle Feng、Jie Yang、Xueqing Fan、Qi Zhang、Yonghai Chai

  DOI：10.1021/acs.orglett.3c01179

  日期：2023.5.19

  Rapid synthesis of saccharides by a chemical method is an efficient way to meet the demand for well-defined glycans to probe their biological functions. Herein, a feasible and convenient strategy for saccharide synthesis was established by introducing a photosensitive fluorous tag at the anomeric position of glycosides. The tag was used not only in polytetrafluoroethylene-assisted rapid purification

  通过化学方法快速合成糖类是满足明确聚糖探测其生物学功能需求的有效途径。在此，通过在糖苷的端基异构位置引入光敏氟标签，建立了一种可行且方便的糖类合成策略。该标签不仅可用于聚四氟乙烯辅助的快速纯化，还可作为碳水化合物还原端的临时保护基团。通过光解对标签进行正交脱保护后，标签保护的糖苷可以转化为新的糖基供体，用于聚合合成。通过结合 β-导向 C-5 羧酸盐糖基化策略，有效地制备了 β-1,4-甘露糖醛酸。