methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-(3,4-O-isopropylidene-2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl)-3,6'-di-O-(propan-1,3-diyl)-β-D-glucopyranoside | 257286-47-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-(3,4-O-isopropylidene-2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl)-3,6'-di-O-(propan-1,3-diyl)-β-D-glucopyranoside
• 英文别名: N-[(1S,3S,4R,6R,7R,8R,15R,16S,20S,21R)-6-methoxy-18,18-dimethyl-21-[(2S,3S,4R,5R,6S)-6-methyl-3,4,5-tris(phenylmethoxy)oxan-2-yl]oxy-4-(phenylmethoxymethyl)-2,5,9,13,17,19,22-heptaoxatetracyclo[13.6.1.03,8.016,20]docosan-7-yl]acetamide
• CAS: 257286-47-8
• 化学式: C₅₅H₆₉NO₁₅
• 分子量: 984.151
• InChiKey: QZVPVHXOGQYXEB-LNSLKGBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  71
• 可旋转键数：
  17
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  158
• 氢给体数：
  1
• 氢受体数：
  15

反应信息

• 作为反应物：
  描述：

  methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-(3,4-O-isopropylidene-2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl)-3,6'-di-O-(propan-1,3-diyl)-β-D-glucopyranoside 在 水 、 溶剂黄146 作用下， 反应 6.0h， 生成 N-[(1S,3S,4R,6R,7R,8R,15R,16R,17S,18R)-4-Benzyloxymethyl-16,17-dihydroxy-6-methoxy-18-((2S,3S,4R,5R,6S)-3,4,5-tris-benzyloxy-6-methyl-tetrahydro-pyran-2-yloxy)-2,5,9,13,19-pentaoxa-tricyclo[13.3.1.0^3,8]nonadec-7-yl]-acetamide
  参考文献：
  名称：

  Constrained H-Type 2 Blood Group Trisaccharide Synthesized in a Bioactive Conformation via Intramolecular Glycosylation

  摘要：

  The methyl glycoside of the II-type 2 trisaccharide 1 was synthesized in a constrained, bioactive conformation via intramolecular aglycon delivery. Computer modeling of the crystal structure of the Ulex europaeus I lectin with a docked H-type 2 trisaccharide suggested that the disaccharide Galp(1-->4)GlcpNAc1-->OCH3 could be tethered in a bioactive conformation if Gal O-6 and GlcNAc O-3 are linked via a three-carbon tether. The ethyl 1-thiogalactopyranoside 13 was used to alkylate the methyl 2-acetamido-2-deoxy glucopyranoside 7, and the resulting dimer was subjected to intramolecular glycosylation following protecting group manipulation. The tethered disaccharide 4 was glycosylated by the activated fucopyranosyl donor 3 to give the protected target molecule 17. Solid-phase binding assays showed that the tethered trisaccharide 2 was 3-fold less active than native II-type 2 trisaccharide 1 when assayed against the U, europaeus I lectin, whereas it was 250 times less active when assayed with the Psophocarpus tetragonolobus II lectin. The observed activities are consistent with published models for H-trisaccharide interactions with Ulex: and Psophocarpus lectins and provide further evidence that suggests reduction of oligosaccharide flexibility by intramolecular tethering provides no significant gain in binding energy.

  DOI：

  10.1021/jo990979a
• 作为产物：
  描述：

  1-硫代-Β-D-乙基半乳糖苷 在 盐酸 、 2,6-二叔丁基-4-甲基吡啶 、 3 A molecular sieve 、 4 A molecular sieve 、 四丁基氟化铵 、 sodium hydride 、 sodium cyanoborohydride 、 对甲苯磺酸 、 DMTST 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 三氟甲烷磺酸甲酯 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 二甲基亚砜 、 N,N-二甲基甲酰胺 为溶剂， 反应 63.5h， 生成 methyl 2-acetamido-6-O-benzyl-2-deoxy-4-O-(3,4-O-isopropylidene-2-O-(2,3,4-tri-O-benzyl-α-L-fucopyranosyl)-β-D-galactopyranosyl)-3,6'-di-O-(propan-1,3-diyl)-β-D-glucopyranoside
  参考文献：
  名称：

  Constrained H-Type 2 Blood Group Trisaccharide Synthesized in a Bioactive Conformation via Intramolecular Glycosylation

  摘要：

  The methyl glycoside of the II-type 2 trisaccharide 1 was synthesized in a constrained, bioactive conformation via intramolecular aglycon delivery. Computer modeling of the crystal structure of the Ulex europaeus I lectin with a docked H-type 2 trisaccharide suggested that the disaccharide Galp(1-->4)GlcpNAc1-->OCH3 could be tethered in a bioactive conformation if Gal O-6 and GlcNAc O-3 are linked via a three-carbon tether. The ethyl 1-thiogalactopyranoside 13 was used to alkylate the methyl 2-acetamido-2-deoxy glucopyranoside 7, and the resulting dimer was subjected to intramolecular glycosylation following protecting group manipulation. The tethered disaccharide 4 was glycosylated by the activated fucopyranosyl donor 3 to give the protected target molecule 17. Solid-phase binding assays showed that the tethered trisaccharide 2 was 3-fold less active than native II-type 2 trisaccharide 1 when assayed against the U, europaeus I lectin, whereas it was 250 times less active when assayed with the Psophocarpus tetragonolobus II lectin. The observed activities are consistent with published models for H-trisaccharide interactions with Ulex: and Psophocarpus lectins and provide further evidence that suggests reduction of oligosaccharide flexibility by intramolecular tethering provides no significant gain in binding energy.

  DOI：

  10.1021/jo990979a

文献信息

• Constrained H-Type 2 Blood Group Trisaccharide Synthesized in a Bioactive Conformation via Intramolecular Glycosylation
  作者：Shirley A. Wacowich-Sgarbi、David R. Bundle

  DOI：10.1021/jo990979a

  日期：1999.12.1

  The methyl glycoside of the II-type 2 trisaccharide 1 was synthesized in a constrained, bioactive conformation via intramolecular aglycon delivery. Computer modeling of the crystal structure of the Ulex europaeus I lectin with a docked H-type 2 trisaccharide suggested that the disaccharide Galp(1-->4)GlcpNAc1-->OCH3 could be tethered in a bioactive conformation if Gal O-6 and GlcNAc O-3 are linked via a three-carbon tether. The ethyl 1-thiogalactopyranoside 13 was used to alkylate the methyl 2-acetamido-2-deoxy glucopyranoside 7, and the resulting dimer was subjected to intramolecular glycosylation following protecting group manipulation. The tethered disaccharide 4 was glycosylated by the activated fucopyranosyl donor 3 to give the protected target molecule 17. Solid-phase binding assays showed that the tethered trisaccharide 2 was 3-fold less active than native II-type 2 trisaccharide 1 when assayed against the U, europaeus I lectin, whereas it was 250 times less active when assayed with the Psophocarpus tetragonolobus II lectin. The observed activities are consistent with published models for H-trisaccharide interactions with Ulex: and Psophocarpus lectins and provide further evidence that suggests reduction of oligosaccharide flexibility by intramolecular tethering provides no significant gain in binding energy.