2,3-di-O-benzyl-4,6-O-benzylidene-1-deoxy-1-(2-oxo-2-phenylethyl)-β-D-mannopyranose | 1072522-97-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-di-O-benzyl-4,6-O-benzylidene-1-deoxy-1-(2-oxo-2-phenylethyl)-β-D-mannopyranose
• 英文别名: 2,3-di-O-benzyl-4,6-O-benzylidene-1-deoxy-1-(2-oxo-2-phenylethyl)-D-mannopyranose
• CAS: 1072522-97-4
• 化学式: C₃₅H₃₄O₆
• 分子量: 550.651
• InChiKey: XQOZBXHNRPNWLC-PYULDIBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.31
• 重原子数：
  41.0
• 可旋转键数：
  10.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  63.22
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  1-苯基-1-三甲基硅氧乙烯 、 2,3-di-O-benzyl-4,6-O-benzylidene-α-D-mannopyranosyl triflate 以 二氯甲烷 为溶剂， 反应 2.0h， 以81.0 mg的产率得到2,3-di-O-benzyl-4,6-O-benzylidene-1-deoxy-1-(2-oxo-2-phenylethyl)-β-D-mannopyranose
  参考文献：
  名称：

  Is Donor−Acceptor Hydrogen Bonding Necessary for 4,6-O-Benzylidene-directed β-Mannopyranosylation? Stereoselective Synthesis of β-C-Mannopyranosides and α-C-Glucopyranosides

  摘要：

  2,3-Di-O-benzyl-4,6-O-benzylidene-thiohexopyranosides, on activation with 1-benzenesulfinyl piperidine and triflic anhydride, react with allyl silanes and stannanes, and with silyl enolethers to give C-glycosides. In the mannose series the beta-isomers are formed selectively whereas the glucose series provides the (alpha-anomers. This selectivity pattern parallels that of O-glycoside formation and eliminates the need to consider donor-acceptor hydrogen bonding in the formation of the O-glycoside.

  DOI：

  10.1021/ol8017038

文献信息

• Stereoselective <i>C</i>-Glycoside Formation with 2-<i>O</i>-Benzyl-4,6-<i>O</i>-benzylidene Protected 3-Deoxy Gluco- and Mannopyranoside Donors: Comparison with <i>O</i>-Glycoside Formation
  作者：Myriame Moumé-Pymbock、David Crich

  DOI：10.1021/jo3011655

  日期：2012.10.19

  mannopyranosyl thioglycosides is highly stereoselective providing the α-C-glycosides in the gluco-series and the β-C-glycosides in the manno-series. Conformational analysis of nucleophilic attack of putative intermediate glycosyl oxocarbenium ions suggests that the observed selectivities for C-glycoside formation can be explained by preferential attack on the opposite face of the oxocarbenium to the C2–H2

  不同于醇的反应Ç -nucleophiles与2- ö -苄基-4,6- ø -亚苄基保护的3-脱氧葡萄糖-和吡喃甘露糖基硫代糖苷是高立体选择性提供所述α- Ç -glycosides在葡萄糖-系列和甘露糖系列中的β- C-糖苷。对假定中间体糖基氧代碳鎓离子亲核攻击的构象分析表明，观察到的 C-糖苷形成选择性可以通过优先攻击氧代碳鎓与 C2-H2 键的相反面来解释，并且与该键的相消相互作用是主要的立体决定因素。有人认为，醇（sp 3）攻击中的空间相互作用-杂化的 O) 和典型的碳基亲核试剂 (sp 2 C) 在氧碳鎓离子上有很大不同，前者不太严重，因此没有先验的理由期望O - 和C -糖基化表现出平行攻击给定氧碳鎓离子的立体选择性。
• Mild Cu(OTf)₂-Mediated C-Glycosylation with Chelation-Assisted Picolinate as a Leaving Group
  作者：Wenjing Ye、Christopher M. Stevens、Peng Wen、Christopher J. Simmons、Weiping Tang

  DOI：10.1021/acs.joc.0c01041

  日期：2020.12.18

  C-glycosylation reactions of glycosyl picolinates with allyltrimethylsilane or silyl enol ethers were devel-oped. Picolinate as a chelation-assisted leaving group could be activated by Cu(OTf)2 and avoided the use of harsh Lewis acids. The glycosylations were operated under mild neutral conditions and gave the corre-sponding C-glycosides in up to 95% yield with moderate to excellent stereoselectivities.