ethyl 3,4,6-tri-O-benzyl-2-O-picolinyl-1-thio-β-D-glucopyranoside | 1083195-76-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3,4,6-tri-O-benzyl-2-O-picolinyl-1-thio-β-D-glucopyranoside
• 英文别名: 3,4,6-tri-O-benzyl-2-O-picolyl-1-thio-β-D-glucopyranose；2-[[(2S,3R,4S,5R,6R)-2-ethylsulfanyl-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl]oxymethyl]pyridine
• CAS: 1083195-76-9
• 化学式: C₃₅H₃₉NO₅S
• 分子量: 585.764
• InChiKey: FGYCEJZBSOLFNC-KJQSSVQNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  42
• 可旋转键数：
  15
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  84.3
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  甲基2,3,4-三-O-苄基-α-D-吡喃葡萄糖苷 、 ethyl 3,4,6-tri-O-benzyl-2-O-picolinyl-1-thio-β-D-glucopyranoside 在 DMTST 作用下， 以 二氯甲烷 为溶剂， 反应 18.0h， 以70%的产率得到methyl 2,3,4-tri-O-benzyl-6-O-(3,4,6-tri-O-benzyl-2-O-picolyl-β-D-glucopyranosyl)-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
• 作为产物：
  描述：

  2-(溴甲基)吡啶氢溴酸盐 、 ethyl 3,4,6-tri-O-benzyl-1-thio-β-D-glucopyranoside 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 0.5h， 以83%的产率得到ethyl 3,4,6-tri-O-benzyl-2-O-picolinyl-1-thio-β-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

• 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.
• Effect of Remote Picolinyl and Picoloyl Substituents on the Stereoselectivity of Chemical Glycosylation
  作者：Jagodige P. Yasomanee、Alexei V. Demchenko

  DOI：10.1021/ja307355n

  日期：2012.12.12

  O-Picolinyl and O-picoloyl groups at remote positions (C-3, C-4, and C-6) can mediate glycosylation reactions by providing high or even complete facial selectivity for the attack of the glycosyl acceptor. The set of data presented herein offers a strong evidence of the intermolecular H-bond tethering between the glycosyl donor and glycosyl acceptor counterparts while providing a practical new methodology for the synthesis of either 1,2-cis or 1,2-trans linkages. Challenging glycosidic linkages including alpha-gluco, beta-manno, and beta-rhamno have seen obtained with high or complete stereocontrol.