benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-3,4,6-tri-O-benzyl-α-D-glucopyranosyl]-3,4,6-tri-O-benzyl-β-D-glucopyranoside | 184882-26-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-3,4,6-tri-O-benzyl-α-D-glucopyranosyl]-3,4,6-tri-O-benzyl-β-D-glucopyranoside
• 英文别名: Glc3Ac4Ac6Ac(a1-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(a1-2)[Bn(-3)][Bn(-4)][Bn(-6)]Glc(b)-O-Bn；[(2R,3R,4R,5R,6R)-3,4-diacetyloxy-6-[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-[(2R,3R,4S,5R,6R)-2,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-5-hydroxyoxan-2-yl]methyl acetate
• CAS: 184882-26-6
• 化学式: C₇₃H₈₀O₁₉
• 分子量: 1261.43
• InChiKey: PKCCQHUGHPYOIS-MHXSEXAUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  92
• 可旋转键数：
  34
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  210
• 氢给体数：
  1
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-3,4,6-tri-O-benzyl-α-D-glucopyranosyl]-3,4,6-tri-O-benzyl-β-D-glucopyranoside 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 0.08h， 生成 (2R,3R,4S,5S,6R)-2-[(2R,3R,4S,5R,6R)-4,5-Bis-benzyloxy-6-benzyloxymethyl-2-((2R,3R,4S,5R,6R)-2,4,5-tris-benzyloxy-6-benzyloxymethyl-tetrahydro-pyran-3-yloxy)-tetrahydro-pyran-3-yloxy]-6-hydroxymethyl-tetrahydro-pyran-3,4,5-triol
  参考文献：
  名称：

  Synthesis of Kojitriose using Silicon-Tethered Glycosidation.

  摘要：

  Reaction of 3,4,6-tri-O-acetyl-beta-D-glucopyranosyl chloride (1) with potassium phenylselenate gave phenyl 3,4,6-tri-O-acetyl-1-seleno-alpha,beta-D-glucopyranoside (2) in 59% yield. Silylation of benzyl 3,4,6-tri-O-benzyl-beta-D-glucopyranoside (4) with ethyl 3,4,6-tri-O-benzyl-2-O-chlorodimethylsilyl-1-thio-beta-D-glucopyranoside gave benzyl 2-O-(3,4,6-tri-O-benzyl-1-S-ethyl-1-thio-beta-D-glucopyranos-2-O-yldimethylsilyl)-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (5) in 35% yield. Reaction of 5 with N-iodosuccinimide in nitromethane gave benzyl 2-O-(3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl)-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (6) in 45% yield. Chlorodimethylsilylation of phenyl 3,4,6-tri-O-acetyl-1-seleno-alpha-D-glucopyranoside (2 alpha) and reaction with 6 gave benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-1-Se-phenyl-1-seleno-alpha-D-glucopyranos-2-O-yldimethylsilyl) -3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl]-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (7) in 82% yield. Intramolecular glycosidation of 7 using N-iodosuccinimide in nitromethane gave benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-alpha-D-glucopyranosyl)-3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl]-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (8) in 45% yield. Deprotection of 8 gave kojitriose (9) in quantitative yield. Chlorodimethylsilylation of 1,3,4,6-tetra-O-benzyl-alpha,beta-D-fructofuranose (10) with dimethyldichlorosilane and pyridine followed by reaction with ethyl 3,4,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (3) gave ethyl 2-O-(1,3,4,6-tetra-O-benzyl- alpha,beta-D-fructofuranosyloxydimethylsilyl)-3,4,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (11) in 85% yield. Chlorodimethylsilylation of 1,3,4,6-tetra-O-benzoyl-alpha-D-fructofuranose (12) with dimethyldichlorosilane and triethylamine followed by reaction with phenyl 3,4,6-tri-O-acetyl-1-thio-alpha-D-glucopyranoside (13) gave phenyl 2-O-(1,3,4,6-tetra-O-benzoyl-alpha-D-fructofuranosyloxydimethylsilyl)-3,4,6-tri-O-acetyl-1-thio-alpha-D-glucopyranoside (14) in 62% yield. Both 11 and 14 failed to undergo intramolecular glycosidation.

  DOI：

  10.3891/acta.chem.scand.50-0931
• 作为产物：
  描述：

  [(2R,3R,4S,5R,6R)-3,4-diacetyloxy-5-[[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-2-[(2R,3R,4S,5R,6R)-2,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-dimethylsilyl]oxy-6-phenylselanyloxan-2-yl]methyl acetate 在 N-碘代丁二酰亚胺 作用下， 以 硝基甲烷 为溶剂， 以45%的产率得到benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-3,4,6-tri-O-benzyl-α-D-glucopyranosyl]-3,4,6-tri-O-benzyl-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of Kojitriose using Silicon-Tethered Glycosidation.

  摘要：

  Reaction of 3,4,6-tri-O-acetyl-beta-D-glucopyranosyl chloride (1) with potassium phenylselenate gave phenyl 3,4,6-tri-O-acetyl-1-seleno-alpha,beta-D-glucopyranoside (2) in 59% yield. Silylation of benzyl 3,4,6-tri-O-benzyl-beta-D-glucopyranoside (4) with ethyl 3,4,6-tri-O-benzyl-2-O-chlorodimethylsilyl-1-thio-beta-D-glucopyranoside gave benzyl 2-O-(3,4,6-tri-O-benzyl-1-S-ethyl-1-thio-beta-D-glucopyranos-2-O-yldimethylsilyl)-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (5) in 35% yield. Reaction of 5 with N-iodosuccinimide in nitromethane gave benzyl 2-O-(3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl)-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (6) in 45% yield. Chlorodimethylsilylation of phenyl 3,4,6-tri-O-acetyl-1-seleno-alpha-D-glucopyranoside (2 alpha) and reaction with 6 gave benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-1-Se-phenyl-1-seleno-alpha-D-glucopyranos-2-O-yldimethylsilyl) -3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl]-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (7) in 82% yield. Intramolecular glycosidation of 7 using N-iodosuccinimide in nitromethane gave benzyl 2-O-[2-O-(3,4,6-tri-O-acetyl-alpha-D-glucopyranosyl)-3,4,6-tri-O-benzyl-alpha-D-glucopyranosyl]-3,4,6-tri-O-benzyl-beta-D-glucopyranoside (8) in 45% yield. Deprotection of 8 gave kojitriose (9) in quantitative yield. Chlorodimethylsilylation of 1,3,4,6-tetra-O-benzyl-alpha,beta-D-fructofuranose (10) with dimethyldichlorosilane and pyridine followed by reaction with ethyl 3,4,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (3) gave ethyl 2-O-(1,3,4,6-tetra-O-benzyl- alpha,beta-D-fructofuranosyloxydimethylsilyl)-3,4,6-tri-O-benzyl-1-thio-beta-D-glucopyranoside (11) in 85% yield. Chlorodimethylsilylation of 1,3,4,6-tetra-O-benzoyl-alpha-D-fructofuranose (12) with dimethyldichlorosilane and triethylamine followed by reaction with phenyl 3,4,6-tri-O-acetyl-1-thio-alpha-D-glucopyranoside (13) gave phenyl 2-O-(1,3,4,6-tetra-O-benzoyl-alpha-D-fructofuranosyloxydimethylsilyl)-3,4,6-tri-O-acetyl-1-thio-alpha-D-glucopyranoside (14) in 62% yield. Both 11 and 14 failed to undergo intramolecular glycosidation.

  DOI：

  10.3891/acta.chem.scand.50-0931