((3aR,4R,6S,7S,7aS)-4-Allyloxy-2,2,6-trimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yloxy)-trimethyl-silane | 311778-83-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((3aR,4R,6S,7S,7aS)-4-Allyloxy-2,2,6-trimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yloxy)-trimethyl-silane
• CAS: 311778-83-3
• 化学式: C₁₅H₂₈O₅Si
• 分子量: 316.47
• InChiKey: KHBXDXLCLDIIBV-ODXJTPSBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  21.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.87
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  ((3aR,4R,6S,7S,7aS)-4-Allyloxy-2,2,6-trimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yloxy)-trimethyl-silane 在 吡啶 、 (1,5-cyclooctadiene)bis(methyldiphenylphosphine) iridium hexafluorophosphate 、 三氟甲磺酸酐 、 三氟化硼乙醚 、 水 、 溶剂黄146 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 mercury dichloride 、 mercury(II) oxide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 1,2-二氯乙烷 、 丙酮 为溶剂， 反应 96.5h， 生成 methyl (2,3,4,6-tetra-O-benzyl-α-D-glucopyranosyl)-(1->4)-(2,3-di-O-benzoyl-α-L-rhamnopyranosyl)-(1->3)-2-acetamido-2-deoxy-4,6-O-isopropylidene-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of the Methyl Glycosides of a Di- and Two Trisaccharide Fragments Specific for theShigella flexneriSerotype 2aO-Antigen

  摘要：

  The stereocontrolled synthesis of methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranoside (EC, 1), methyl alpha-L-rhamnopyranosyl-(1-->3)-[alpha-D-glucopyra- osyl-(1-->4)]-alpha-L-rhamnopyranoside (B(E)C, 3) and methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->3)-2-acetamido-2-deoxy-beta-D-glucopyranoside (ECD, 4) is described; these constitute the methyl glycosides of branched and linear fragments of the O-specific polysaccharide of Shigella flexneri serotype 2a. Emphasis was put on the construction of the 1,2-cis EC glycosidic linkage resulting in the selection of 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl fluoride (8) as the donor. Condensation of methyl 2,3-O-isopropylidene-4-O-trimethylsilyloside-alpha-L-rhamnopyranoside (11) and 8 afforded the fully protected alpha E-disaccharide 20, as a common intermediate in the synthesis of 1 and 3, together with the corresponding beta E-anomer 21. Deacetalation and regioselective benzoylation of 20, followed by glycosylation with 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (15) afforded the branched trisaccharide 25. Full deprotection of 20 and 25 afforded the targets 1 and 3, respectively. The corresponding beta E-disaccharide, namely, methyl beta-D-glucopyranosyl-(1-->4)-a-L-rhamnopyranoside (PEC, 2) was prepared analogously from 21. Two routes to trisaccharide 4 were considered. Route 1 involved the coupling of a precursor to residue E and a disaccharide CD. Route 2 was based on the condensation of an appropriate EC donor and a precursor to residue D. The former route afforded a 1:2 mixture of the alpha E and PE condensation products which could not be separated, neither at this stage, nor after deacetalation. In route 2, the required alpha E-anomer was isolated at the disaccharide stage and transformed into 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl-(1-->4)-2,3-di-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (48) as the EC donor. Methyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-beta-D-glucopyran-oside (19) was preferred to its benzylidene analogue as the precursor to residue D. Condensation of 19 and 48 and stepwise deprotection of the glycosylation product afforded the target 4.

  DOI：

  10.1080/07328300008544123
• 作为产物：
  描述：

  三甲基氯硅烷 、 allyl 2,3-O-isopropylidene-α-L-rhamnopyranoside 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以96%的产率得到((3aR,4R,6S,7S,7aS)-4-Allyloxy-2,2,6-trimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yloxy)-trimethyl-silane
  参考文献：
  名称：

  Synthesis of the Methyl Glycosides of a Di- and Two Trisaccharide Fragments Specific for theShigella flexneriSerotype 2aO-Antigen

  摘要：

  The stereocontrolled synthesis of methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranoside (EC, 1), methyl alpha-L-rhamnopyranosyl-(1-->3)-[alpha-D-glucopyra- osyl-(1-->4)]-alpha-L-rhamnopyranoside (B(E)C, 3) and methyl alpha-D-glucopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->3)-2-acetamido-2-deoxy-beta-D-glucopyranoside (ECD, 4) is described; these constitute the methyl glycosides of branched and linear fragments of the O-specific polysaccharide of Shigella flexneri serotype 2a. Emphasis was put on the construction of the 1,2-cis EC glycosidic linkage resulting in the selection of 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl fluoride (8) as the donor. Condensation of methyl 2,3-O-isopropylidene-4-O-trimethylsilyloside-alpha-L-rhamnopyranoside (11) and 8 afforded the fully protected alpha E-disaccharide 20, as a common intermediate in the synthesis of 1 and 3, together with the corresponding beta E-anomer 21. Deacetalation and regioselective benzoylation of 20, followed by glycosylation with 2,3,4-tri-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (15) afforded the branched trisaccharide 25. Full deprotection of 20 and 25 afforded the targets 1 and 3, respectively. The corresponding beta E-disaccharide, namely, methyl beta-D-glucopyranosyl-(1-->4)-a-L-rhamnopyranoside (PEC, 2) was prepared analogously from 21. Two routes to trisaccharide 4 were considered. Route 1 involved the coupling of a precursor to residue E and a disaccharide CD. Route 2 was based on the condensation of an appropriate EC donor and a precursor to residue D. The former route afforded a 1:2 mixture of the alpha E and PE condensation products which could not be separated, neither at this stage, nor after deacetalation. In route 2, the required alpha E-anomer was isolated at the disaccharide stage and transformed into 2,3,4,6-tetra-O-benzyl-alpha-D-glucopyranosyl-(1-->4)-2,3-di-O-benzoyl-alpha-L-rhamnopyranosyl trichloroacetimidate (48) as the EC donor. Methyl 2-acetamido-2-deoxy-4,6-O-isopropylidene-beta-D-glucopyran-oside (19) was preferred to its benzylidene analogue as the precursor to residue D. Condensation of 19 and 48 and stepwise deprotection of the glycosylation product afforded the target 4.

  DOI：

  10.1080/07328300008544123

文献信息

• 8-(Methyltosylaminoethynyl)-1-naphthyl (MTAEN) Glycosides: Potent Donors in Glycosides Synthesis
  作者：Si-Yu Zhou、Xin-Ping Hu、Hui-Juan Liu、Qing-Ju Zhang、Jin-Xi Liao、Yuan-Hong Tu、Jian-Song Sun

  DOI：10.1021/acs.orglett.1c04102

  日期：2022.1.21

  efficient glycosylation protocol has been established. The MTAEN glycosylation protocol exhibits the merits of shelf-stable donors, mild catalytic promotion conditions, considerably extended substrate scope encompassing both free alcohols, silylated alcohols, nucleobases, primary amides, and C-type nucleophile acceptors, and applicability to various one-pot strategies for highly efficient synthesis of oligosaccharides

  以 8-(methyltosylaminoethynyl)-1-naphthyl (MTAEN) 糖苷为供体，建立了一种新颖高效的糖基化方案。MTAEN 糖基化方案具有货架稳定供体、温和的催化促进条件、大大扩展底物范围（包括游离醇、甲硅烷基化醇、核碱基、伯酰胺和C型亲核受体）的优点，并适用于各种一锅策略用于高效合成寡糖，例如正交一锅法、单催化剂一锅法和受体反应性控制一锅法。