methyl 2,3,4-tri-O-benzyl-6-O-(4,6-di-O-benzyl-2,3-O-carbonyl-β-D-glucopyranosyl)-(1->6)-α-D-glucopyranoside | 864967-07-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-6-O-(4,6-di-O-benzyl-2,3-O-carbonyl-β-D-glucopyranosyl)-(1->6)-α-D-glucopyranoside
• 英文别名: methyl (4,6-di-O-benzyl-2,3-O-carbonyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；(3aR,4R,6R,7R,7aS)-4-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-7-phenylmethoxy-6-(phenylmethoxymethyl)-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-2-one
• CAS: 864967-07-7
• 化学式: C₄₉H₅₂O₁₂
• 分子量: 832.945
• InChiKey: SVCPEZIJNUXLFO-GPOQTLLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  61
• 可旋转键数：
  20
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  119
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-benzyl-6-O-(4,6-di-O-benzyl-2,3-O-carbonyl-β-D-glucopyranosyl)-(1->6)-α-D-glucopyranoside 在 lithium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(4,6-di-O-benzyl-β-D-glucopyranosyl)-(1->6)-α-D-glucopyranoside
  参考文献：
  名称：

  Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a trans-Fused 2,3-O-Carbonate Group

  摘要：

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.

  DOI：

  10.1021/jo0508999
• 作为产物：
  描述：

  phenyl 4,6-di-O-benzyl-1-thio-β-D-glucopyranoside 在 1-(苯基亚硫酰基)哌啶 、 三氟甲磺酸酐 、 三乙胺 、 2,4,6-三叔丁基嘧啶 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 2.5h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(4,6-di-O-benzyl-2,3-O-carbonyl-β-D-glucopyranosyl)-(1->6)-α-D-glucopyranoside
  参考文献：
  名称：

  Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a trans-Fused 2,3-O-Carbonate Group

  摘要：

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.

  DOI：

  10.1021/jo0508999

文献信息

• Lewis Acids as α-Directing Additives in Glycosylations by Using 2,3-<i>O</i>-Carbonate-Protected Glucose and Galactose Thioglycoside Donors Based on Preactivation Protocol
  作者：Yiqun Geng、Qi Qin、Xin-Shan Ye

  DOI：10.1021/jo3002084

  日期：2012.6.15

  Catalytic or stoichiometric amounts of Lewis acids were found to be very effective a-directing additives in the stereoselective glycosylations of diverse 2,3-O-carbonate-protected glucose and galactose thioglycoside donors by preactivation protocol. The poor stereoselectivities of 4,6-di-O-acetyl-2,3-O-carbonate protected thioglycoside donors in glycosyl coupling reactions were greatly improved, and excellent alpha-stereoselectivities were achieved by the addition of 0.2 equiv of BF3 center dot OEt2. On the other hand, the beta-selectivities of 4,6-di-O-benzyl-2,3-O-carbonate-protected thioglucoside donor toward glycosylations were reversed completely to the alpha-selectivities by the use of 1 equiv of SnCl4, making the stereoselectivity controllable. Furthermore, the poor stereoselectivities of 4,6-di-O-benzyl-2,3-O-carbonate-protected thiogalactoside donor in glycosylations were also improved by using SnCl4 as additive.
• Stereocontrolled Formation of β-Glucosides and Related Linkages in the Absence of Neighboring Group Participation:  Influence of a <i>trans</i>-Fused 2,3-<i>O</i>-Carbonate Group
  作者：David Crich、Prasanna Jayalath

  DOI：10.1021/jo0508999

  日期：2005.9.1

  [GRAPHICS]Phenyl 4,6-di-O-benzyl-2,3-O-carbonyl-beta-D-glucothiopyranoside and the regiosiomeric phenyl 2,6-di-O-benzyl-3,4-O-carbonyl-beta-D-glucothiopyranoside were prepared and studied as glucosyl donors at -60 degrees C in dichloromethane with preactivation by 1-benzenesulfinyl piperidine before addition of the acceptor alcohol. The 2,3-O-carbonate protected donor showed moderate to excellent beta-selectivity under these conditions depending on the acceptor employed, thereby providing a means for 1,2-trans-equatorial glycosidic bonds without recourse to neighboring group participation and its associated problem of ortho ester formation. In contrast, the 3,4-O-carbonate protected donor showed moderate to no beta-selectivity under the conditions employed. The results obtained in this study with carbonate protected glucopyranosyl donors are contrasted with those obtained previously in the manno- and rhamnopyranosyl series when the 2,3-O-carbonate protected is (x-selective and the 3,4-O-carbonate is beta-selective.