methyl 2,3,4-tri-O-benzyl-6-O-(2,4-di-O-benzyl-3-O-picoloyl-β-L-rhamnopyranosyl)-α-D-glucopyranoside | 1415590-86-1

• 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-(2,4-di-O-benzyl-3-O-picoloyl-β-L-rhamnopyranosyl)-α-D-glucopyranoside
• CAS: 1415590-86-1
• 化学式: C₅₄H₅₇NO₁₁
• 分子量: 896.047
• InChiKey: RSRYDGJDRMPMRG-MADDXVMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.67
• 重原子数：
  66.0
• 可旋转键数：
  21.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  122.26
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  (2S,3R,4R,5R,6R)-4,5-Bis-benzyloxy-6-benzyloxymethyl-2-methoxy-tetrahydro-pyran-3-ol 、 methyl 2,3,4-tri-O-benzyl-6-O-(2,4-di-O-benzyl-3-O-picoloyl-β-L-rhamnopyranosyl)-α-D-glucopyranoside 在 DMTST 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以90%的产率得到methyl 3,4,6-tri-O-benzyl-2-O-(2,4-di-O-benzyl-3-O-picoloyl-β-L-rhamnopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Effect of Remote Picolinyl and Picoloyl Substituents on the Stereoselectivity of Chemical Glycosylation

  摘要：

  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.

  DOI：

  10.1021/ja307355n
• 作为产物：
  描述：

  ethyl 4-O-tert-butyldimethylsilyl-1-thio-β-L-rhamnopyranoside 在 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium hydride 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,2-二氯乙烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 4.75h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(2,4-di-O-benzyl-3-O-picoloyl-β-L-rhamnopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Effect of Remote Picolinyl and Picoloyl Substituents on the Stereoselectivity of Chemical Glycosylation

  摘要：

  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.

  DOI：

  10.1021/ja307355n

文献信息

• Hydrogen bond activated glycosylation under mild conditions
  作者：Ke Xiao、Yongxin Hu、Yongyong Wan、XinXin Li、Qin Nie、Hao Yan、Liming Wang、Jinxi Liao、Deyong Liu、Yuanhong Tu、Jiansong Sun、Jeroen D. C. Codée、Qingju Zhang

  DOI：10.1039/d1sc05772c

  日期：——

  Benefitting from the mild reaction conditions, this new hydrogen bond-mediated glycosylation system in combination with a hydrogen bond-mediated aglycon delivery system provides a reliable method for the synthesis of challenging phenolic glycosides. In addition, a chemoselective glycosylation procedure was developed using different imidate donors (trichloroacetimidates, N-phenyl trifluoroacetimidates, N-4-nitrophenyl

  在这里，我们报告了一种新的糖基化系统，用于使用糖基N-苯基三氟乙酰亚胺 (PTFAI) 供体和带电的硫脲氢键供体催化剂高效和立体选择性地形成糖苷键。糖基化方案具有广泛的底物范围、可控的立体选择性、良好至极好的产率和异常温和的催化条件。得益于温和的反应条件，这种新的氢键介导的糖基化系统与氢键介导的糖苷配基递送系统相结合，为合成具有挑战性的酚苷提供了可靠的方法。此外，使用不同的酰亚胺供体（三氯乙酰亚胺，N-苯基三氟乙酰亚胺酯、N -4-硝基苯基三氟乙酰亚胺酯、苯并恶唑基亚胺酸酯和 6-硝基-苯并噻唑基亚胺酸酯），并通过新的一锅单催化剂策略应用于三糖合成。