ethyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside | 870195-62-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(a1-3)[Bn(-2)][Bn(-4)][Bn(-6)]Man(a)-SEt；(2R,3S,4S,5R,6R)-2-ethylsulfanyl-3,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-4-[(2R,3R,4S,5R,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxane
• CAS: 870195-62-3
• 化学式: C₆₃H₆₈O₁₀S
• 分子量: 1017.29
• InChiKey: PMZRIJWGSYYDHW-FYUAFKCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  74
• 可旋转键数：
  27
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  118
• 氢给体数：
  0
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside 在 palladium on activated charcoal 盐酸 、 N-碘代丁二酰亚胺 、 4 A molecular sieve 、 氢气 、 silver trifluoromethanesulfonate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 3.5h， 生成 methyl α-D-glucopyranosyl-(1->3)-α-D-mannopyranosyl-(1->2)-3-deoxy-α-D-arabino-hexopyranoside
  参考文献：
  名称：

  Synthesis of monodeoxy analogues of the trisaccharide α-d-Glcp-(1→3)-α-d-Manp-(1→2)-α-d-ManpOMe recognised by Calreticulin/Calnexin

  摘要：

  Six (3,4,4',6',3" or 6")-monodeoxy analogues of the title trisaccharide (1-6) have been prepared utilising monodeoxy monosaccharide precursors. The reducing end deoxy derivatives were synthesised by N-iodosuccinimide/silver trifluoromethanesulfonate (NIS/AgOTf)-promoted couplings of a common disaccharide thioglycoside donor 10 to suitably protected monodeoxy acceptors 9 and 12, affording trisaccharides, which after deprotection yielded target structures 1 and 2. The non-reducing end deoxy derivatives could similarly be produced by halide-assisted glycosylations of a common disaccharide acceptor 17 with monodeoxy glycosyl bromide donors (obtained from thioglycosides 18 and 20) to yield, after removal of protecting groups, target trisaccharides 3 and 4. The analogues with the deoxy function in the middle mannose residue, were obtained through orthogonal halide-assisted coupling of tetrabenzyl-glucopyranosyl bromide to monodeoxy thioglycoside acceptors to give thioglycoside disaccharides, which subsequently were used as donors in NIS/AgOTf-promoted couplings to a common 2-hydroxy-mannose acceptor 15 to afford trisaccharides; deprotection yielded the final target compounds 5 and 6. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.carres.2006.03.015
• 作为产物：
  描述：

  ethyl 6-O-acetyl-1-thio-α-D-mannopyranoside 在 盐酸 、 4 A molecular sieve 、 camphor-10-sulfonic acid 、 sodium methylate 、 sodium hydride 、 三苯基氧化膦 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 102.42h， 生成 ethyl 2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl-(1->3)-2,4,6-tri-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  四糖α-D-Glcp-（1→3）-α-D-Manp-（1→2）-α-D-Manp-（1→2）-α-D-的合成被钙网蛋白/钙粘蛋白识别的Manp。

  摘要：

  使用嵌段合成方法有效地合成了标题化合物作为其甲基糖苷。6-O-乙酰基-2,3,4-三-O-苄基-α-D-吡喃葡萄糖基碘化物与乙基2-O-乙酰基-4,6-二-O-苄基-1-硫代烃之间的卤化物辅助糖基化使用三苯基氧化膦作为促进剂的β-α-D-甘露吡喃糖苷以完全的α-选择性产生了高产率的二糖结构单元。事实证明，该化合物的过苄基化衍生物是出色的供体，它以NIS / AgOTf促进的偶联方式提供88％的受保护目标四糖与已知的甲基二甘露糖苷受体。然后通过催化氢解脱保护得到目标化合物，总产率为47％。

  DOI：

  10.1016/j.carres.2005.09.001

文献信息

• Glycosyl iodides. History and recent advances
  作者：Peter J. Meloncelli、Alan D. Martin、Todd L. Lowary

  DOI：10.1016/j.carres.2009.02.032

  日期：2009.6

  The use of glycosyl iodides as an effective method for the preparation of glycosides has had a recent resurgence in carbohydrate chemistry, despite its early roots in which these species were believed to be of limited use. Renewed interest in these species as glycosylating agents has been spurred by their demonstrated utility in the stereoselective preparation of O-glycosides, and other glycosylic compounds. This review provides a brief historical account followed by an examination of the use of glycosyl iodides in the synthesis of oligosaccharicles and other glycomimetics, including C-glycosylic compounds, glycosyl azides and N-glycosides. (C) 2009 Elsevier Ltd. All rights reserved.
• Synthesis of monodeoxy analogues of the trisaccharide α-d-Glcp-(1→3)-α-d-Manp-(1→2)-α-d-ManpOMe recognised by Calreticulin/Calnexin
  作者：Emiliano Gemma、Martina Lahmann、Stefan Oscarson

  DOI：10.1016/j.carres.2006.03.015

  日期：2006.7

  Six (3,4,4',6',3" or 6")-monodeoxy analogues of the title trisaccharide (1-6) have been prepared utilising monodeoxy monosaccharide precursors. The reducing end deoxy derivatives were synthesised by N-iodosuccinimide/silver trifluoromethanesulfonate (NIS/AgOTf)-promoted couplings of a common disaccharide thioglycoside donor 10 to suitably protected monodeoxy acceptors 9 and 12, affording trisaccharides, which after deprotection yielded target structures 1 and 2. The non-reducing end deoxy derivatives could similarly be produced by halide-assisted glycosylations of a common disaccharide acceptor 17 with monodeoxy glycosyl bromide donors (obtained from thioglycosides 18 and 20) to yield, after removal of protecting groups, target trisaccharides 3 and 4. The analogues with the deoxy function in the middle mannose residue, were obtained through orthogonal halide-assisted coupling of tetrabenzyl-glucopyranosyl bromide to monodeoxy thioglycoside acceptors to give thioglycoside disaccharides, which subsequently were used as donors in NIS/AgOTf-promoted couplings to a common 2-hydroxy-mannose acceptor 15 to afford trisaccharides; deprotection yielded the final target compounds 5 and 6. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of the tetrasaccharide α-d-Glcp-(1→3)-α-d-Manp-(1→2)-α-d-Manp-(1→2)-α-d-Manp recognized by Calreticulin/Calnexin
  作者：Emiliano Gemma、Martina Lahmann、Stefan Oscarson

  DOI：10.1016/j.carres.2005.09.001

  日期：2005.11

  The title compound as its methyl glycoside was efficiently synthesized using a block synthesis approach. Halide-assisted glycosidations between 6-O-acetyl-2,3,4-tri-O-benzyl-alpha-D-glucopyranosyl iodide and ethyl 2-O-acetyl-4,6-di-O-benzyl-1-thio-alpha-D-mannopyranoside using triphenylphosphine oxide as promoter yielded, with complete alpha-selectivity, a disaccharide building block in high yield. The

  使用嵌段合成方法有效地合成了标题化合物作为其甲基糖苷。6-O-乙酰基-2,3,4-三-O-苄基-α-D-吡喃葡萄糖基碘化物与乙基2-O-乙酰基-4,6-二-O-苄基-1-硫代烃之间的卤化物辅助糖基化使用三苯基氧化膦作为促进剂的β-α-D-甘露吡喃糖苷以完全的α-选择性产生了高产率的二糖结构单元。事实证明，该化合物的过苄基化衍生物是出色的供体，它以NIS / AgOTf促进的偶联方式提供88％的受保护目标四糖与已知的甲基二甘露糖苷受体。然后通过催化氢解脱保护得到目标化合物，总产率为47％。