2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate | 409060-32-8

• 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-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)][Bn(-6)]Gal(b1-4)[Bn(-2)][Bn(-3)][Bn(-6)]Glc(b)-O-C(NH)CCl3；[(2S,3R,4S,5R,6R)-3,4-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-5-[(2S,3R,4S,5S,6R)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-yl]oxyoxan-2-yl] 2,2,2-trichloroethanimidate
• CAS: 409060-32-8
• 化学式: C₆₃H₆₄Cl₃NO₁₁
• 分子量: 1117.56
• InChiKey: NCJHGTQPCUGWRT-VVDHWLILSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.4
• 重原子数：
  78
• 可旋转键数：
  27
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  125
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate 、 methyl (6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-glucopyranosyl)-(1->2)-6,7-di-O-acetyl-L-glycero-α-D-manno-heptopyranoside 在 三氟甲磺酸三甲基硅酯 、 MS AW-300 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.0h， 以24%的产率得到methyl (2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl)-(1->4)-(2,3,6-tri-O-benzyl-α-D-glucopyranosyl)-(1->3)-[6-O-acetyl-2-azido-3,4-di-O-benzyl-2-deoxy-α-D-glucopyranosyl-(1->2)]-6,7-di-O-acetyl-L-glycero-α-D-manno-heptopyranoside
  参考文献：
  名称：

  通过 2-O-取代的庚糖衍生物的区域选择性 3-O-甲硅烷基化合成 2,3-二-O-取代的庚糖结构

  摘要：

  2-O-苄基 (Bn) 庚糖 (Hep)、甲基 6,7-二-O-乙酰基-2-O-苄基-L-甘油-α-D-甘露糖-庚糖苷的 3,4-二醇衍生物（ 3)，用三乙基甲硅烷基 (TES) 和叔丁基二甲基甲硅烷基 (TBDMS) 氯化物处理，分别区域选择性地形成 3-O-甲硅烷基醚 4 和 6。为了检查 2-O-取代二糖的 3,4-二醇的甲硅烷基化是否也产生相应的 3-O-甲硅烷基化二糖，我们通过偶联 Hep 2-合成了 α-GlcN3-(1⇄2)-Hep 11a OH 受体 9 与 GlcN3 三氯乙酰亚胺 10. 正如使用 2-O-Bn Hep 3 获得的结果所预期的那样，用 TESCl 处理 α-GlcN3-(1⇄2)-Hep-3,4-二醇 14，然后进行乙酰化仅得到 3-O-TES 15。通过甲硅烷基化/乙酰化（不分离 15）和随后的酸水解，将化合物 14 转化为 3-OH 受体 16。通过将二糖

  DOI：

  10.1002/ejoc.200300652
• 作为产物：
  描述：

  溴甲苯 、 alkaline earth salt of/the/ methylsulfuric acid 在 ammonium cerium(IV) nitrate 、 四丁基碘化铵 、 sodium hydride 作用下， 以 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 9.0h， 生成 2,3,4,6-tetra-O-benzyl-β-D-galactopyranosyl-(1->4)-2,3,6-tri-O-benzyl-β-D-glucopyranosyl trichloroacetimidate
  参考文献：
  名称：

  Synthesis of α-lactosyl-(1→3)-l-glycero-α-d-manno-heptopyranoside, a partial oligosaccharide structure expressed within the lipooligosaccharide produced by Neisseria gonorrhoeae strain 15253

  摘要：

  The glycosyl donor, hepta-O-benzyl-beta-lactosyl trichloroacetimidate (4) was prepared by treating hepta-O-benzyl-lactose with trichloroacetonitrile in the presence of potassium carbonate. The acceptor, methyl 2-O-benzyl-4,6-O-benzylidene-7,8-dideoxy-alpha-D-manno-oct-7-enopyranoside (8) was synthesized by hydrolysis of a 3,4-butane diacetal of methyl L-glycero-alpha-D-manno-oct-enopyranoside and subsequent benzylidenation, Glycosidation of the donor 4 with the acceptor 8 in 1,4-dioxane using Me3SiOTf as a promoter for I h at room temperature gave methyl (2,3,4,6-tetra-O-benzyl-beta-D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-alpha-D-glucopyranosyl)-(1-->3)-2-O-benzyl-4,6-O-benzylidene-7,8-dideoxy-alpha-D-manno-oct-7-enopyranoside (9) as a major product (59%). The oct-enopyranoside moiety of the trisaccharide 9 was converted to a heptopyranoside (80%) by oxidative cleavage with OsO4-NaIO4 and subsequent reduction. Hydrogenolysis of the resulting trisaccharide and subsequent acetylation gave the peracetate of alpha-lactosyl-(1-->3)-Hep. Deacetylation of the peracetate afforded the title trisaccharide. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0008-6215(01)00282-8

文献信息

• Synthesis of α-lactosyl-(1→3)-l-glycero-α-d-manno-heptopyranoside, a partial oligosaccharide structure expressed within the lipooligosaccharide produced by Neisseria gonorrhoeae strain 15253
  作者：Kazuyuku Ishii、Hiroyuki Kubo、Ryohei Yamasaki

  DOI：10.1016/s0008-6215(01)00282-8

  日期：2002.1

  The glycosyl donor, hepta-O-benzyl-beta-lactosyl trichloroacetimidate (4) was prepared by treating hepta-O-benzyl-lactose with trichloroacetonitrile in the presence of potassium carbonate. The acceptor, methyl 2-O-benzyl-4,6-O-benzylidene-7,8-dideoxy-alpha-D-manno-oct-7-enopyranoside (8) was synthesized by hydrolysis of a 3,4-butane diacetal of methyl L-glycero-alpha-D-manno-oct-enopyranoside and subsequent benzylidenation, Glycosidation of the donor 4 with the acceptor 8 in 1,4-dioxane using Me3SiOTf as a promoter for I h at room temperature gave methyl (2,3,4,6-tetra-O-benzyl-beta-D-galactopyranosyl)-(1-->4)-(2,3,6-tri-O-benzyl-alpha-D-glucopyranosyl)-(1-->3)-2-O-benzyl-4,6-O-benzylidene-7,8-dideoxy-alpha-D-manno-oct-7-enopyranoside (9) as a major product (59%). The oct-enopyranoside moiety of the trisaccharide 9 was converted to a heptopyranoside (80%) by oxidative cleavage with OsO4-NaIO4 and subsequent reduction. Hydrogenolysis of the resulting trisaccharide and subsequent acetylation gave the peracetate of alpha-lactosyl-(1-->3)-Hep. Deacetylation of the peracetate afforded the title trisaccharide. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Synthesis of a 2,3-Di-O-substituted Heptose Structure by Regioselective 3-O-Silylation of a 2-O-Substituted Heptose Derivative
  作者：Kazuyuki Ishii、Yasuaki Esumi、Youhei Iwasaki、Ryohei Yamasaki

  DOI：10.1002/ejoc.200300652

  日期：2004.3

  (Hep), methyl 6,7-di-O-acetyl-2-O-benzyl-L-glycero-α-D-manno-heptopyranoside (3), was treated with both triethylsilyl (TES) and tert-butyldimethylsilyl (TBDMS) chlorides to regioselectively form the 3-O-silyl ethers 4 and 6, respectively. To examine whether silylation of the 3,4-diol of a 2-O-substituted disaccharide also gives the corresponding 3-O-silylated disaccharide, we synthesized α-GlcN3-(1⇄2)-Hep

  2-O-苄基 (Bn) 庚糖 (Hep)、甲基 6,7-二-O-乙酰基-2-O-苄基-L-甘油-α-D-甘露糖-庚糖苷的 3,4-二醇衍生物（ 3)，用三乙基甲硅烷基 (TES) 和叔丁基二甲基甲硅烷基 (TBDMS) 氯化物处理，分别区域选择性地形成 3-O-甲硅烷基醚 4 和 6。为了检查 2-O-取代二糖的 3,4-二醇的甲硅烷基化是否也产生相应的 3-O-甲硅烷基化二糖，我们通过偶联 Hep 2-合成了 α-GlcN3-(1⇄2)-Hep 11a OH 受体 9 与 GlcN3 三氯乙酰亚胺 10. 正如使用 2-O-Bn Hep 3 获得的结果所预期的那样，用 TESCl 处理 α-GlcN3-(1⇄2)-Hep-3,4-二醇 14，然后进行乙酰化仅得到 3-O-TES 15。通过甲硅烷基化/乙酰化（不分离 15）和随后的酸水解，将化合物 14 转化为 3-OH 受体 16。通过将二糖