benzyl 3-deoxy-4-S-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-4-thio-β-D-glycero-pentopyranosid-2-ulose | 1191092-87-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: benzyl 3-deoxy-4-S-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-4-thio-β-D-glycero-pentopyranosid-2-ulose
• 英文别名: benzyl per-O-acetyl-3-deoxy-4-S-(β-D-Galp)-4-thio-pentopyranosid-2-ulose
• CAS: 1191092-87-1
• 化学式: C₂₆H₃₂O₁₂S
• 分子量: 568.599
• InChiKey: MIPLPSXTKMAPKP-KJPVENLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  39.0
• 可旋转键数：
  10.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  149.96
• 氢给体数：
  0.0
• 氢受体数：
  13.0

反应信息

• 作为反应物：
  描述：

  benzyl 3-deoxy-4-S-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-4-thio-β-D-glycero-pentopyranosid-2-ulose 在 sodium tetrahydroborate 、 水 、 三乙胺 作用下， 以 甲醇 为溶剂， 反应 2.0h， 生成 2-propyl 3-deoxy-4-S-(β-D-galactopyranosyl)-4-thio-α-D-lyxo-hexopyranoside
  参考文献：
  名称：

  Synthesis of pentopyranosyl-containing thiodisaccharides. Inhibitory activity against β-glycosidases

  摘要：

  beta-(1 -> 4)-Thiodisaccharides formed by a pentopyranose unit as reducing or non reducing end have been synthesized using a sugar enone derived from a hexose or pentose as Michael acceptor of a 1-thiopentopyranose or 1-thiohexopyranose derivatives. Thus, 2-propyl per-O-acetyl-3-deoxy-4-S-(beta-D-Xylp)-4-thiohexopyranosid-2-ulose (3) and benzyl per-O-acetyl-3-deoxy-4-S-(beta-D-Galp)-4-thiopentopyranosid-2-ulose (11) were obtained in almost quantitative yields. The carbonyl function of these uloses was reduced with NaBH4 or K-Selectride, and the stereochemical course of the reduction was highly dependent on the reaction temperature, reducing agent and solvent. Unexpectedly, reduction of 3 with NaBH4-THF at 0 degrees C gave a 3-deoxy-4-S-(beta-D-Xylp)-4-thio-alpha-D-ribo-hexopyranoside derivative (6) as major product (74% yield), with isomerization of the sulfur-substituted C-4 stereocenter of the pyranone. Reduction of 11 gave always as major product the benzyl 3-deoxy-4-S-(Galp)-4-thio-beta-D-threo-pentopyranoside derivative 14, which was the only product isolated (80% yield) in the reduction with K-Selectride in THF at -78 degrees C. Deprotection of 14 and its epimer at C-2 (13) afforded, respectively the free thiodisaccharides 19 and 18. They displayed strong inhibitory activity against the beta-galactosidase from Escherichia coli. Thus, compound 18 proved to be a non-competitive inhibitor of the enzyme (K-i = 0.80 mM), whereas 19 was a mixed-type inhibitor (K-i = 32 mu M). (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2009.07.055
• 作为产物：
  描述：

  2,3,4,6-四-O-乙酰基-1-硫代-BETA-D-吡喃半乳糖 、 (2S)-2-benzyloxy-2H-pyran-3(6H)-one 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 benzyl 3-deoxy-4-S-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyl)-4-thio-β-D-glycero-pentopyranosid-2-ulose
  参考文献：
  名称：

  Synthesis of pentopyranosyl-containing thiodisaccharides. Inhibitory activity against β-glycosidases

  摘要：

  beta-(1 -> 4)-Thiodisaccharides formed by a pentopyranose unit as reducing or non reducing end have been synthesized using a sugar enone derived from a hexose or pentose as Michael acceptor of a 1-thiopentopyranose or 1-thiohexopyranose derivatives. Thus, 2-propyl per-O-acetyl-3-deoxy-4-S-(beta-D-Xylp)-4-thiohexopyranosid-2-ulose (3) and benzyl per-O-acetyl-3-deoxy-4-S-(beta-D-Galp)-4-thiopentopyranosid-2-ulose (11) were obtained in almost quantitative yields. The carbonyl function of these uloses was reduced with NaBH4 or K-Selectride, and the stereochemical course of the reduction was highly dependent on the reaction temperature, reducing agent and solvent. Unexpectedly, reduction of 3 with NaBH4-THF at 0 degrees C gave a 3-deoxy-4-S-(beta-D-Xylp)-4-thio-alpha-D-ribo-hexopyranoside derivative (6) as major product (74% yield), with isomerization of the sulfur-substituted C-4 stereocenter of the pyranone. Reduction of 11 gave always as major product the benzyl 3-deoxy-4-S-(Galp)-4-thio-beta-D-threo-pentopyranoside derivative 14, which was the only product isolated (80% yield) in the reduction with K-Selectride in THF at -78 degrees C. Deprotection of 14 and its epimer at C-2 (13) afforded, respectively the free thiodisaccharides 19 and 18. They displayed strong inhibitory activity against the beta-galactosidase from Escherichia coli. Thus, compound 18 proved to be a non-competitive inhibitor of the enzyme (K-i = 0.80 mM), whereas 19 was a mixed-type inhibitor (K-i = 32 mu M). (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2009.07.055

文献信息

• Design and Synthesis of 2-Acetamido-2,3-dideoxythiodisaccharides via Diastereoselective Conjugate Addition to Sugar Enone <i>O</i>-Acetyl Oximes. Galactosidase Inhibition Studies
  作者：Lucas Dada、Verónica E. Manzano、Oscar Varela

  DOI：10.1021/acs.orglett.8b02692

  日期：2018.10.5

  3-dideoxy-(1→4)-thiodisaccharides was the conjugate addition of a 1-thiogalactose derivative to E and Z acetyl oximes derived from sugar enones. This reaction was shown to be completely diastereoselective for both the formation of the thioglycosidic linkage and the configuration of acetyl oxime. The thiodisaccharides have been designed as inhibitors of the β-galactosidase from E. coli, and they have been shown

  新合成2-乙酰氨基-2,3-二脱氧-（1→4）-硫代二糖的关键步骤是将1-硫代半乳糖衍生物共轭加成自糖烯酮的E和Z乙酰肟。对于硫糖苷键的形成和乙酰基肟的构型，该反应被证明是完全非对映选择性的。硫二糖已被设计为大肠杆菌的β-半乳糖苷酶的抑制剂，并且已被证明能够成功满足此类要求。