3,4,6-tri-O-acetyl-2-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-α-D-mannopyranosyl tricholoacetimidate | 187140-07-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,6-tri-O-acetyl-2-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-α-D-mannopyranosyl tricholoacetimidate
• 英文别名: (2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-(1->2)-3,4,6-tri-O-acetyl-α-D-mannopyranosyl trichloroacetimidate；Bz(-2)[Bz(-3)][Bz(-4)][Bz(-6)]Man(a1-2)Man3Ac4Ac6Ac(a)-O-C(NH)CCl3；[(2R,3R,4S,5S,6R)-3,4,5-tribenzoyloxy-6-[(2R,3S,4S,5R,6R)-4,5-diacetyloxy-6-(acetyloxymethyl)-2-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl]oxyoxan-2-yl]methyl benzoate
• CAS: 187140-07-4
• 化学式: C₄₈H₄₄Cl₃NO₁₈
• 分子量: 1029.23
• InChiKey: UUEZHAGDXIUEIT-DLTYFHBUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.9
• 重原子数：
  70
• 可旋转键数：
  24
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  245
• 氢给体数：
  1
• 氢受体数：
  19

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-acetyl-2-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-α-D-mannopyranosyl tricholoacetimidate 、 octyl 2-O-benzoyl-4-O-(1-fluoro-1,1,3,3-tetraisopropyl-1,3-disiloxane-3-yl)-3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-α-D-mannospyranoside 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以52%的产率得到octyl 2-O-benzoyl-4-O-(1-fluoro-1,1,3,3-tetraisopropyl-1,3-disiloxane-3-yl)-3-O-(2,3,4,6-tetra-O-benzyl-α-D-galactopyranosyl)-6-O-[2-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-3,4,6-tri-O-acetyl-α-D-mannopyranosyl]-α-D-mannospyranoside
  参考文献：
  名称：

  Synthesis of α-galactosylated fragments related to the core-structure of the GPI anchor of Trypanosoma brucei

  摘要：

  A series of octyl glycosides di- to tetrasaccharides related to the CPI anchor of Trypanosoma brucei was prepared. Treatment of octyl 2-O-benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-alpha-D-mannopyranoside with ethyl 2,3,4,6-tetra-O-benzyl-1-thio-beta-D-galactopyranoside under activation with bromine and silver trifluoromethanesulfonate afforded the alpha-linked disaccharide octyl 2-O-benzoyl-3-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)-4,6-O-(1,1,3,3-tetraisoprogyl-1,3-disiloxane-1,3-diyl)-alpha-D-mannospyranoside, the siloxane ring of which was regioselectively opened with a HF-pyridine complex to give the disaccharide acceptor octyl 3-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)- 2-O-benzoyl-4-O-(3-fluoro-1,1,3,3-tetraisopropyl-1,3-disiloxane-3-yl)-alpha-D-mannopyranoside (4). Mannosylation of 4 with benzobromomannose (7), followed by fluoride catalyzed desilylation gave the trisaccharide octyl 2-O-benzoyl-6-O-(2,3,4,6-tetra-O-benzoyl-alpha-D-mannopyranosyl)-3-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)-alpha-D-mannospyranoside, which was deblocked via the deacylated intermediate octyl 3-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)-6-O-(alpha-D-mannopranosyl)-alpha-D-mannospyranoside to afford the octyl glycoside trisaccharide octyl 3-O-(alpha-D-galactopyranosyl)-6-O-(alpha-D-mannopyranosyl)-alpha-D-mannospyranoside. Glycosylation of 4 with 3,4,6-tri-O-acetyl-2-O-(2,3,4,6-tetra-O-benzoyl-alpha-D-mannopyranosyl)-alpha-D-mannopyranosyl trichloroacetimidate resulted in the tetrasaccharide octyl 2-O-benzoyl-4-O-(1-fluoro-1,1,3,3-tetraisopropyl-1,3-disiloxane-3-yl)-3-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)- 6-O-[2-O-(2,3,4,6-tetra-O-benzoyl-alpha-D-mannopyranosyl)-3,4,6-tri-O-acetyl-alpha-D-mannopyranosyl]- alpha-D-mannospyranoside, sequential desilylation, deacylation and debenzylation, respectively, of which via the intermediate octyl 2-O-benzoyl-3-O-(2,3,4,6-tetra-O-benzyl-alpha-D-galactopyranosyl)-6-O-[2-O-(2,3,4,6-tetra-O-benzoyl-alpha-D-mannopyranosyl)-3,4,6-tri-O-acetyl-alpha-D-mannopyranosyl]-alpha-D-mannospyranoside afforded the octyl glycoside tetrasaccharide octyl 3-O-(alpha-D-galactopyranosyl)-6-O-[2-O-(alpha-D-mannopyranosyl]-alpha-D-mannopyranosyl]-alpha-D-mannospyranoside. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(00)00071-9
• 作为产物：
  描述：

  1,3,4,6-四-氧-乙酰-Β-D-吡啶甘露糖 在 2,4,6-三甲基吡啶 、 3 A molecular sieve 、 silver trifluoromethanesulfonate 、 乙酸肼 、 potassium carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 7.25h， 生成 3,4,6-tri-O-acetyl-2-O-(2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl)-α-D-mannopyranosyl tricholoacetimidate
  参考文献：
  名称：

  Synthesis of octyl O- and S-glycosides related to the GPI anchor of Trypanosoma brucei and their in vitro galactosylation by trypanosomal α-galactosyltransferases

  摘要：

  Octyl O- and S-glycosides of mono- to tri-saccharides related to the core structure alpha-D-Manp-(1-->2)-alpha-D-Manp-(1-->6)-alpha-D-Manp of the GPI anchor of Trypanosoma brucei have been prepared via regioselective protodesilylation and glycodesilylation of octyl O- and S-glycosides of 2-O-benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-alpha-D-mannopyranoside. The synthetic saccharides have been used as substrates for enzymatic alpha-galactosylation with membrane fractions of bloodstream forms of T. brucei strain 427 variants MIT at 1.4, MIT at 1.2, and MIT at 1.5, respectively. (C) 1996 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(96)00215-7

文献信息

• Synthesis of octyl S-glycosides of tri- to pentasaccharide fragments related to the GPI anchor of Trypanosoma brucei
  作者：Ralf Dettmann、Thomas Ziegler

  DOI：10.1016/j.carres.2011.08.001

  日期：2011.11

  The three oligosaccharide octyl-S-glycosides Man-alpha 1,6-Man-alpha 1,4-GlcNH(2)-alpha 1,S-Octyl (19), Man-alpha 1,6-(Gal-alpha 1,3)Man-alpha 1,4-GlcNH(2)-alpha 1,S-Octyl (27) and Man-alpha 1,2-Man-alpha 1,6-(Gal-alpha 1,3)Man-alpha 1,4-GlcNH(2)-alpha 1,S-Octyl (37), related to the GPI anchor of Trypanosoma brucei were prepared by a stepwise and block-wise approach from octyl 2-azido-2-deoxy-3,6-di-O-benzyl-1-thio-alpha-D-glucopyranoside (8) and octyl 2-O-benzoyl-4,6-O-(1,1,3,3-tetraisopropyl-1,3-disiloxane-1,3-diyl)-1-thio-alpha-D-mannopyransoside (9). Glucosamine derivative 8 was obtained from 1,3,4,6-tetra-O-acetyl-2-azido-2-desoxy-beta-D-glucopyranose (1) in five steps. Mannoside 9 was converted into the corresponding imidate 12 and coupled with 8 to give disaccharide octyl-S-glycoside 13 which was further mannosylated to afford trisaccharide 19 upon deprotection. Likewise, mannoside 9 was galactosylated, converted into the corresponding imidate and coupled with 8 to give trisaccharide 25. Mannosylation of the latter afforded tetrasaccharide 27 upon deprotection. Condensation of 25 with disaccharide imidate 35 gave, upon deprotection of the intermediates, the corresponding pentasaccharide octyl-S-glycoside 37. Saccharides 19, 27 and 37 are suitable substrates for studying the enzymatic glycosylation pattern of the GPI anchor of T. brucei. (C) 2011 Elsevier Ltd. All rights reserved.