methyl 3,4,6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,4,6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
• 英文别名: methyl O-(3,4,6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-(1-6)-O-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1-6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside；[(2R,3R,4S,5R,6R)-4,5-dibenzoyloxy-2-[[(2R,3R,4S,5R,6R)-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)-3-(pyridin-2-ylmethoxy)oxan-2-yl]oxymethyl]-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]oxan-3-yl] benzoate
• 化学式: C₈₈H₈₇NO₁₉
• 分子量: 1462.65
• InChiKey: VXIHXJWZRBOBFW-AEMICMCCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13
• 重原子数：
  108
• 可旋转键数：
  38
• 环数：
  13.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  212
• 氢给体数：
  0
• 氢受体数：
  20

反应信息

• 作为产物：
  描述：

  4,5-dihydrothiazol-2-yl 2,3,4-tri-O-benzoyl-6-O-(3,4,6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-1-thio-β-D-glucopyranoside 、 甲基2,3,4-三-O-苄基-α-D-吡喃葡萄糖苷 在 silver trifluoromethanesulfonate 作用下， 以 DCE 为溶剂， 反应 17.0h， 以91%的产率得到methyl 3,4,6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl-(1->6)-(2,3,4-tri-O-benzoyl-β-D-glucopyranosyl)-(1->6)-2,3,4-tri-O-benzyl-α-D-glucopyranoside
  参考文献：
  名称：

  How the Arming Participating Moieties can Broaden the Scope of Chemoselective Oligosaccharide Synthesis by Allowing the Inverse Armed−Disarmed Approach

  摘要：

  A new method for stereocontrolled glycosylation and chemoselective oligosaccharide synthesis has been developed. It has been determined that complete 1,2-trans selectivity can be achieved with the use of a 2-O-picolyl moiety, a novel neighboring group that is capable of efficient participation via a six-membered intermediate. The application of the picolyl concept to glycosidations of thioimidoyl, thioglycosyl, and trichloroacetimidoyl glycosyl donors is demonstrated. The picolyl moiety also retains the glycosyl donor in the armed state, as opposed to conventional acyl participating moieties. We name this new approach the "inverse armed-disarmed" strategy, because it allows for the chemoselective introduction of a 1,2-trans glycosidic linkage prior to other linkages. In the context of the oligosaccharide synthesis, the strategy provides trans-trans and trans-cis patterned oligosaccharides as opposed to classic Fraser-Reid's armed-disarmed approach leading to cis-trans and cis-cis linkages.

  DOI：

  10.1021/jo801551r

文献信息

• Development of an Arming Participating Group for Stereoselective Glycosylation and Chemoselective Oligosaccharide Synthesis
  作者：James T. Smoot、Papapida Pornsuriyasak、Alexei V. Demchenko

  DOI：10.1002/anie.200502694

  日期：2005.11.4
• How the Arming Participating Moieties can Broaden the Scope of Chemoselective Oligosaccharide Synthesis by Allowing the Inverse Armed−Disarmed Approach
  作者：James T. Smoot、Alexei V. Demchenko

  DOI：10.1021/jo801551r

  日期：2008.11.21

  A new method for stereocontrolled glycosylation and chemoselective oligosaccharide synthesis has been developed. It has been determined that complete 1,2-trans selectivity can be achieved with the use of a 2-O-picolyl moiety, a novel neighboring group that is capable of efficient participation via a six-membered intermediate. The application of the picolyl concept to glycosidations of thioimidoyl, thioglycosyl, and trichloroacetimidoyl glycosyl donors is demonstrated. The picolyl moiety also retains the glycosyl donor in the armed state, as opposed to conventional acyl participating moieties. We name this new approach the "inverse armed-disarmed" strategy, because it allows for the chemoselective introduction of a 1,2-trans glycosidic linkage prior to other linkages. In the context of the oligosaccharide synthesis, the strategy provides trans-trans and trans-cis patterned oligosaccharides as opposed to classic Fraser-Reid's armed-disarmed approach leading to cis-trans and cis-cis linkages.