methoxyethyl 2,6-di-O-benzoyl 3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-β-D-glucopyranoside | 1139754-17-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methoxyethyl 2,6-di-O-benzoyl 3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-β-D-glucopyranoside
• 英文别名: [(3aS,4R,6S,7R,7aS)-7-benzoyloxy-6-[(2R,3R,4S,5R,6R)-5-benzoyloxy-2-(benzoyloxymethyl)-6-(2-methoxyethoxy)-4-[(2S,3S,4R,5R,6S)-6-methyl-3,4,5-tris(phenylmethoxy)oxan-2-yl]oxyoxan-3-yl]oxy-2,2-dimethyl-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl]methyl benzoate
• CAS: 1139754-17-8
• 化学式: C₇₃H₇₆O₂₀
• 分子量: 1273.39
• InChiKey: ADPWUASMFUWBJG-MSUSHYBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.6
• 重原子数：
  93
• 可旋转键数：
  31
• 环数：
  11.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  216
• 氢给体数：
  0
• 氢受体数：
  20

反应信息

• 作为反应物：
  描述：

  methoxyethyl 2,6-di-O-benzoyl 3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-β-D-glucopyranoside 在 水 、 溶剂黄146 作用下， 反应 4.0h， 以86%的产率得到methoxyethyl 2,6-di-O-benzoyl 3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-β-D-galactopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Regioselective synthesis of a glycomimetic trisaccharide of Sialyl Lewis (sLex)

  摘要：

  Sialyl Lewis (sLe(x)) is the smallest naturally occurring carbohydrate ligand that binds to E-Selectin on the activated endothelium. We report here the total synthesis of acetic acid-sLe(x) analog (12), for testing as a therapeutic agent. Methoxyethyl 4-O-(3,4-O-isopropylidene-beta-D-galactopyranosyl)-beta-D-glucopyranoside (3) was prepared starting from the methoxyethyl-beta-D-lactoside (2), which was selectively benzoylated to give the methoxyethyl 2,6-di-O-benzoyl-4-beta-(2,6-di-O-benzoyl-3,4-0-isopropylidene-beta-D-galactopyranosyl)-beta-D-glucopyranoside (4). Glycosylation of acceptor 4 with methyl 2,3,4-tri-O-benzyl-1-thio-beta-L-fucopyranoside (5) in the presence of cupric bromide and tetrabutylammonium bromide afforded the corresponding methoxyethyl 2,6-di-O-benzyl-3-beta-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-4-0-(2,6-di-O-benzyl-3,4-O-isopropylidene-beta-D-galactopyranosyl)-P-D-glucopyranoside (6). Selective removal of the 4 '',6 ''-O-isopropylidene group from 6 gave the deprotected trisaccharide 7. The regioselective esterification of O-3 '' of trisaccharide 8 (obtained from the dibutylstannylene derivative of 7) with benzyl-2-bromoacetate and tetrabutylammonium bromide afforded the 3 ''-O-carbobenzyloxymethyl trisaccharide derivative 9, which on saponification and hydrogenolysis with palladium-charcoal afforded the target trisaccharide 12 glycomimetic of Sialyl Lewis (sLe(x)) trisaccharide omitting the sialic acid moiety.

  DOI：

  10.1016/j.carres.2008.11.019
• 作为产物：
  描述：

  甲基-2,3,4-三-O-苄基-1-硫代-β-L-岩藻糖苷 、 methoxyethyl 2,6-di-O-benzoyl-4-O-(2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-β-D-glucopyranoside 在 四丁基溴化铵 、 copper(ll) bromide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.5h， 以77%的产率得到methoxyethyl 2,6-di-O-benzoyl 3-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-4-O-(2,6-di-O-benzoyl-3,4-O-isopropylidene-β-D-galactopyranosyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Regioselective synthesis of a glycomimetic trisaccharide of Sialyl Lewis (sLex)

  摘要：

  Sialyl Lewis (sLe(x)) is the smallest naturally occurring carbohydrate ligand that binds to E-Selectin on the activated endothelium. We report here the total synthesis of acetic acid-sLe(x) analog (12), for testing as a therapeutic agent. Methoxyethyl 4-O-(3,4-O-isopropylidene-beta-D-galactopyranosyl)-beta-D-glucopyranoside (3) was prepared starting from the methoxyethyl-beta-D-lactoside (2), which was selectively benzoylated to give the methoxyethyl 2,6-di-O-benzoyl-4-beta-(2,6-di-O-benzoyl-3,4-0-isopropylidene-beta-D-galactopyranosyl)-beta-D-glucopyranoside (4). Glycosylation of acceptor 4 with methyl 2,3,4-tri-O-benzyl-1-thio-beta-L-fucopyranoside (5) in the presence of cupric bromide and tetrabutylammonium bromide afforded the corresponding methoxyethyl 2,6-di-O-benzyl-3-beta-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-4-0-(2,6-di-O-benzyl-3,4-O-isopropylidene-beta-D-galactopyranosyl)-P-D-glucopyranoside (6). Selective removal of the 4 '',6 ''-O-isopropylidene group from 6 gave the deprotected trisaccharide 7. The regioselective esterification of O-3 '' of trisaccharide 8 (obtained from the dibutylstannylene derivative of 7) with benzyl-2-bromoacetate and tetrabutylammonium bromide afforded the 3 ''-O-carbobenzyloxymethyl trisaccharide derivative 9, which on saponification and hydrogenolysis with palladium-charcoal afforded the target trisaccharide 12 glycomimetic of Sialyl Lewis (sLe(x)) trisaccharide omitting the sialic acid moiety.

  DOI：

  10.1016/j.carres.2008.11.019

文献信息

• Regioselective synthesis of a glycomimetic trisaccharide of Sialyl Lewis (sLex)
  作者：Sameh E. Soliman、Rafik W. Bassily、Ramadan I. El-Sokkary、Joseph Banoub、Mina A. Nashed

  DOI：10.1016/j.carres.2008.11.019

  日期：2009.2

  Sialyl Lewis (sLe(x)) is the smallest naturally occurring carbohydrate ligand that binds to E-Selectin on the activated endothelium. We report here the total synthesis of acetic acid-sLe(x) analog (12), for testing as a therapeutic agent. Methoxyethyl 4-O-(3,4-O-isopropylidene-beta-D-galactopyranosyl)-beta-D-glucopyranoside (3) was prepared starting from the methoxyethyl-beta-D-lactoside (2), which was selectively benzoylated to give the methoxyethyl 2,6-di-O-benzoyl-4-beta-(2,6-di-O-benzoyl-3,4-0-isopropylidene-beta-D-galactopyranosyl)-beta-D-glucopyranoside (4). Glycosylation of acceptor 4 with methyl 2,3,4-tri-O-benzyl-1-thio-beta-L-fucopyranoside (5) in the presence of cupric bromide and tetrabutylammonium bromide afforded the corresponding methoxyethyl 2,6-di-O-benzyl-3-beta-(2,3,4-tri-O-benzyl-alpha-L-fucopyranosyl)-4-0-(2,6-di-O-benzyl-3,4-O-isopropylidene-beta-D-galactopyranosyl)-P-D-glucopyranoside (6). Selective removal of the 4 '',6 ''-O-isopropylidene group from 6 gave the deprotected trisaccharide 7. The regioselective esterification of O-3 '' of trisaccharide 8 (obtained from the dibutylstannylene derivative of 7) with benzyl-2-bromoacetate and tetrabutylammonium bromide afforded the 3 ''-O-carbobenzyloxymethyl trisaccharide derivative 9, which on saponification and hydrogenolysis with palladium-charcoal afforded the target trisaccharide 12 glycomimetic of Sialyl Lewis (sLe(x)) trisaccharide omitting the sialic acid moiety.