2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1-4)-O-(2,3,6-tri-O-acetyl-β-D-glucopyranosyl)-(1-4)-2,6-di-O-benzyl-3-deoxy-α-D-ribo-hexopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-α-D-ribo-hexopyranoside | 216572-34-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1-4)-O-(2,3,6-tri-O-acetyl-β-D-glucopyranosyl)-(1-4)-2,6-di-O-benzyl-3-deoxy-α-D-ribo-hexopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-α-D-ribo-hexopyranoside
• CAS: 216572-34-8
• 化学式: C₆₆H₇₈O₂₆
• 分子量: 1287.33
• InChiKey: GSNVFGMCWHEMKW-PBIIESADSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.74
• 重原子数：
  92.0
• 可旋转键数：
  26.0
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  294.86
• 氢给体数：
  0.0
• 氢受体数：
  26.0

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1-4)-O-(2,3,6-tri-O-acetyl-β-D-glucopyranosyl)-(1-4)-2,6-di-O-benzyl-3-deoxy-α-D-ribo-hexopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-α-D-ribo-hexopyranoside 在 sodium methylate 作用下， 以 甲醇 、 乙二醇二甲醚 为溶剂， 反应 5.0h， 以64%的产率得到α-D-glucopyranosyl-(1-4)-O-β-D-glucopyranosyl-(1-4)-2,6-di-O-benzyl-3-deoxy-α-D-ribo-hexopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-α-D-ribo-hexopyranoside
  参考文献：
  名称：

  The Synthesis of Four Dideoxygenated Analogues of β-Maltosyl-(1→4)-Trehalose

  摘要：

  Four derivatives of beta-maltosyl-(1 -->4)-trehalose were prepared, each with two deoxy functions in one of the constitutive disaccharide building blocks. 2,3-Di-O-acetyl-4,6-dideoxy-4,6-diiodo-alpha-D-galactopyranosyl-(1-->4) -1,2,3,6-tetra-O-acetyl-D-glucopyranose (3) was employed as a precursor for the 4'",6'" -dideoxygenated tetrasaccharide 9: coupling of 3 with 2,3,6-tri-O-benzyl-alpha-D-glucopyranosyl 2,3,6-tri-O-benzylidene-alpha-D-glucopyranoside (4) furnished the tetrasaccharide 5 which was deiodinated and deprotected to yield the target tetrasaccharide 9. Secondly, the dideoxygenated maltose derivative 3-deoxy-4,6-O-isopropylidene-2-O-pivaloyl-alpha-D-glucopyranosyl-(1-->4)-1,6- anhydro-3-deoxy-2-O-pivaloyl-beta-D-glucopyranose (10) was ring-opened to the anomeric acetate 11. A [2+2] block synthesis with 4 in TMS triflate mediated glycosylation gave a tetrasaccharide which was deprotected to the 3 ",3'"- dideoxygenated analogue of beta-maltosyl-(1 -->4)-trehalose. For the third tetrasaccharide, 2,3,2',3'-tetra-O-benzyl-alpha,alpha-trehalose was iodinated at the primary positions and deiodinated in the presence of palladium-on-carbon, then this acceptor was selectively glycosylated with hepta-O-acetyl-maltosyl bromide (20). Removal of protective groups furnished the maltosyl trehalose tetrasaccharide deoxygenated at positions C-6 and C-6'. To prepare a 3,3'-dideoxygenated trehalose, the free hydroxyl groups of 2-O-benzyl-4,6-O-(R)-benzylidene-alpha-D-glucopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-alpha-D-glucopryanoside (25) were reduced by Barton-McCombie deoxygenation. One of the benzylidene groups was opened reductively with sodium cyanoborohydride. The resulting free hydroxyl group at the 4'-position was glycosylated in a Koenigs-Knorr reaction with 20 to yield the 3,3'-dideoxygenated tetrasaccharide 32, the fourth target oligosaccharide, after deprotection.

  DOI：

  10.1080/07328309808001900
• 作为产物：
  描述：

  2-O-benzyl-4,6-O-(R)-benzylidene-3-O-(imidazol-1-yl-thiocarbonyl)-α-D-glucopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-3-O-(imidazol-1-yl-thiocarbonyl)-α-D-glucopyranoside 在 盐酸 、 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile 、 三正丁基氢锡 、 silver trifluoromethanesulfonate 、 sodium cyanoborohydride 、 1,1,3,3-四甲基脲 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 34.0h， 生成 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1-4)-O-(2,3,6-tri-O-acetyl-β-D-glucopyranosyl)-(1-4)-2,6-di-O-benzyl-3-deoxy-α-D-ribo-hexopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-α-D-ribo-hexopyranoside
  参考文献：
  名称：

  The Synthesis of Four Dideoxygenated Analogues of β-Maltosyl-(1→4)-Trehalose

  摘要：

  Four derivatives of beta-maltosyl-(1 -->4)-trehalose were prepared, each with two deoxy functions in one of the constitutive disaccharide building blocks. 2,3-Di-O-acetyl-4,6-dideoxy-4,6-diiodo-alpha-D-galactopyranosyl-(1-->4) -1,2,3,6-tetra-O-acetyl-D-glucopyranose (3) was employed as a precursor for the 4'",6'" -dideoxygenated tetrasaccharide 9: coupling of 3 with 2,3,6-tri-O-benzyl-alpha-D-glucopyranosyl 2,3,6-tri-O-benzylidene-alpha-D-glucopyranoside (4) furnished the tetrasaccharide 5 which was deiodinated and deprotected to yield the target tetrasaccharide 9. Secondly, the dideoxygenated maltose derivative 3-deoxy-4,6-O-isopropylidene-2-O-pivaloyl-alpha-D-glucopyranosyl-(1-->4)-1,6- anhydro-3-deoxy-2-O-pivaloyl-beta-D-glucopyranose (10) was ring-opened to the anomeric acetate 11. A [2+2] block synthesis with 4 in TMS triflate mediated glycosylation gave a tetrasaccharide which was deprotected to the 3 ",3'"- dideoxygenated analogue of beta-maltosyl-(1 -->4)-trehalose. For the third tetrasaccharide, 2,3,2',3'-tetra-O-benzyl-alpha,alpha-trehalose was iodinated at the primary positions and deiodinated in the presence of palladium-on-carbon, then this acceptor was selectively glycosylated with hepta-O-acetyl-maltosyl bromide (20). Removal of protective groups furnished the maltosyl trehalose tetrasaccharide deoxygenated at positions C-6 and C-6'. To prepare a 3,3'-dideoxygenated trehalose, the free hydroxyl groups of 2-O-benzyl-4,6-O-(R)-benzylidene-alpha-D-glucopyranosyl 2-O-benzyl-4,6-O-(R)-benzylidene-alpha-D-glucopryanoside (25) were reduced by Barton-McCombie deoxygenation. One of the benzylidene groups was opened reductively with sodium cyanoborohydride. The resulting free hydroxyl group at the 4'-position was glycosylated in a Koenigs-Knorr reaction with 20 to yield the 3,3'-dideoxygenated tetrasaccharide 32, the fourth target oligosaccharide, after deprotection.

  DOI：

  10.1080/07328309808001900