phenyl 2-deoxy-3-O-p-methoxybenzyl-2-phthalimido-1-thio-β-D-galactopyranoside | 362614-08-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2-deoxy-3-O-p-methoxybenzyl-2-phthalimido-1-thio-β-D-galactopyranoside
• 英文别名: 2-[(2S,3R,4R,5R,6R)-5-hydroxy-6-(hydroxymethyl)-4-[(4-methoxyphenyl)methoxy]-2-phenylsulfanyloxan-3-yl]isoindole-1,3-dione
• CAS: 362614-08-2
• 化学式: C₂₈H₂₇NO₇S
• 分子量: 521.591
• InChiKey: JZGOPSNCYPALSK-MOBZEUQDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  37
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  131
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 phenyl 2-deoxy-3-O-p-methoxybenzyl-2-phthalimido-1-thio-β-D-galactopyranoside 在 吡啶 作用下， 反应 8.0h， 以99%的产率得到phenyl 4,6-di-O-acetyl-2-deoxy-3-O-p-methoxybenzyl-2-phthalimido-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  A HIGHLY EFFICIENT TOTAL SYNTHETIC ROUTE TO α-SERIES GANGLIOSIDES: GM1α, GD1α, AND GT1α1-2

  摘要：

  A highly efficient total synthetic route to alpha -series gangliosides GM1 alpha, GD1 alpha and GT1 alpha is described. The suitably protected gangliotriose (GgOse3) derivatives, i.e., 2-(trimethylsilyl)ethyl (2-acetamido-2-deoxy-3-O-p-methoxybenzyl-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1 -->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (8) and the corresponding III3-levulinoyl derivative (9), were regioselectively glycosylated with the phenyl 2-thioglycoside of N-acetylneuraminic acid (Neu5Ac) promoted by N-iodosuccinimide (NIS)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) or trifluoromethanesulfonic acid (TfOH) in acetonitrile, to give the desired alpha -Neu5Ac-(2-->6)-gangliotriose (III(6)Neu5AcGgOse3) derivatives as the major products (11 and 12). The p-methoxybenzyl (MPM) group in 11 or the levulinoyl group in 12 was selectively removed, and the resulting 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2-nonulopyranosylonate)-(2-->6)-(2-acetamido-2-deoxy-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (13), a key glycosyl acceptor, was systematically glycosylated with the galactose donor (14), alpha -Neu5Ac-(2-->3)-galactuse donor (15) and alpha -Neu5Ac-(2-->8)-alpha -Neu5Ac-(2-->3)-galactose donor (20) to give the protected GM1 alpha (16, 70%), GD1 alpha (17, 80%) and GT1 alpha (21, 87%) oligosaccharides, respectively, which can be converted to the target gangliosides by the introduction of ceramide and then complete deprotection.

  DOI：

  10.1081/car-100103959
• 作为产物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-β-D-galactopyranoside 在 三氟化硼乙醚 、 sodium methylate 、 二正丁基氧化锡 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 35.0h， 生成 phenyl 2-deoxy-3-O-p-methoxybenzyl-2-phthalimido-1-thio-β-D-galactopyranoside
  参考文献：
  名称：

  A HIGHLY EFFICIENT TOTAL SYNTHETIC ROUTE TO α-SERIES GANGLIOSIDES: GM1α, GD1α, AND GT1α1-2

  摘要：

  A highly efficient total synthetic route to alpha -series gangliosides GM1 alpha, GD1 alpha and GT1 alpha is described. The suitably protected gangliotriose (GgOse3) derivatives, i.e., 2-(trimethylsilyl)ethyl (2-acetamido-2-deoxy-3-O-p-methoxybenzyl-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1 -->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (8) and the corresponding III3-levulinoyl derivative (9), were regioselectively glycosylated with the phenyl 2-thioglycoside of N-acetylneuraminic acid (Neu5Ac) promoted by N-iodosuccinimide (NIS)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) or trifluoromethanesulfonic acid (TfOH) in acetonitrile, to give the desired alpha -Neu5Ac-(2-->6)-gangliotriose (III(6)Neu5AcGgOse3) derivatives as the major products (11 and 12). The p-methoxybenzyl (MPM) group in 11 or the levulinoyl group in 12 was selectively removed, and the resulting 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2-nonulopyranosylonate)-(2-->6)-(2-acetamido-2-deoxy-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (13), a key glycosyl acceptor, was systematically glycosylated with the galactose donor (14), alpha -Neu5Ac-(2-->3)-galactuse donor (15) and alpha -Neu5Ac-(2-->8)-alpha -Neu5Ac-(2-->3)-galactose donor (20) to give the protected GM1 alpha (16, 70%), GD1 alpha (17, 80%) and GT1 alpha (21, 87%) oligosaccharides, respectively, which can be converted to the target gangliosides by the introduction of ceramide and then complete deprotection.

  DOI：

  10.1081/car-100103959

文献信息

• A HIGHLY EFFICIENT TOTAL SYNTHETIC ROUTE TO α-SERIES GANGLIOSIDES: GM1α, GD1α, AND GT1α1-2
  作者：Hiromi Ito、Hideharu Ishida、Makoto Kiso

  DOI：10.1081/car-100103959

  日期：2001.3.31

  A highly efficient total synthetic route to alpha -series gangliosides GM1 alpha, GD1 alpha and GT1 alpha is described. The suitably protected gangliotriose (GgOse3) derivatives, i.e., 2-(trimethylsilyl)ethyl (2-acetamido-2-deoxy-3-O-p-methoxybenzyl-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1 -->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (8) and the corresponding III3-levulinoyl derivative (9), were regioselectively glycosylated with the phenyl 2-thioglycoside of N-acetylneuraminic acid (Neu5Ac) promoted by N-iodosuccinimide (NIS)-trimethylsilyl trifluoromethanesulfonate (TMSOTf) or trifluoromethanesulfonic acid (TfOH) in acetonitrile, to give the desired alpha -Neu5Ac-(2-->6)-gangliotriose (III(6)Neu5AcGgOse3) derivatives as the major products (11 and 12). The p-methoxybenzyl (MPM) group in 11 or the levulinoyl group in 12 was selectively removed, and the resulting 2-(trimethylsilyl)ethyl (methyl 5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-D-glycero-alpha -D-galacto-2-nonulopyranosylonate)-(2-->6)-(2-acetamido-2-deoxy-beta -D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-beta -D-galactopyranosyl)-(1-->4)-2,3,6-tri-O-benzyl-beta -D-glucopyranoside (13), a key glycosyl acceptor, was systematically glycosylated with the galactose donor (14), alpha -Neu5Ac-(2-->3)-galactuse donor (15) and alpha -Neu5Ac-(2-->8)-alpha -Neu5Ac-(2-->3)-galactose donor (20) to give the protected GM1 alpha (16, 70%), GD1 alpha (17, 80%) and GT1 alpha (21, 87%) oligosaccharides, respectively, which can be converted to the target gangliosides by the introduction of ceramide and then complete deprotection.