methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-6-O-picolinyl-β-D-glucopyranosyl)-α-D-glucopyranoside | 1415590-74-7

• 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-(2,3,4-tri-O-benzyl-6-O-picolinyl-β-D-glucopyranosyl)-α-D-glucopyranoside
• 英文别名: 2-[[(2R,3R,4S,5R,6R)-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxymethyl]pyridine
• CAS: 1415590-74-7
• 化学式: C₆₁H₆₅NO₁₁
• 分子量: 988.187
• InChiKey: RDMKVRXTPRNFGW-CZPKAMCTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.4
• 重原子数：
  73
• 可旋转键数：
  26
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  114
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  2-(溴甲基)吡啶氢溴酸盐 在 sodium hydride 、 palladium(II) bromide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 14.0h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-6-O-picolinyl-β-D-glucopyranosyl)-α-D-glucopyranoside 、 methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-6-O-picolinyl-α-D-glucopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  6-O-Picolinyl and 6-O-Picoloyl Building Blocks As Glycosyl Donors with Switchable Stereoselectivity

  摘要：

  Remote 6-O-picolinyl or 6-O-picoloyl substituents often provide high beta-selectivity due to H-bond-mediated aglycone delivery (HAD). Herein it has been demonstrated that if the nitrogen atom of the 6-O-picolinyl or picoloyl moiety is temporarily blocked by coordination to a metal center (Pd), it cannot engage in HAD-mediated beta-glycosylation. Hence, the stereoselectivity of 6-O-picolinyl/picoloyl-assisted glycosylations can be "switched" to alpha-selectivity.

  DOI：

  10.1021/acs.orglett.5b02110

文献信息

• Coordination chemistry approach to the long-standing challenge of stereocontrolled chemical glycosylation
  作者：Papapida Pornsuriyasak、Cornelia Vetter、Sophon Kaeothip、Michael Kovermann、Jochen Balbach、Dirk Steinborn、Alexei V. Demchenko

  DOI：10.1039/b903942b

  日期：——

  This study clearly demonstrates that a multi-dentate metal coordination to the leaving group, along with O-5 and/or a protecting group at O-6, has a strong effect on the stereoselectivity of chemical glycosylation.

  这项研究清楚地表明，离去基团上的多位金属配位以及 O-5 和/或 O-6 上的保护基对化学糖基化的立体选择性有很大影响。
• 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.