phenylthio 6-O-acetyl-2,3-di-O-benzyl-α-D-mannopyranoside | 1421832-62-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenylthio 6-O-acetyl-2,3-di-O-benzyl-α-D-mannopyranoside
• 英文别名: phenyl 6-O-acetyl-2,3-di-O-benzyl-1-thio-α-D-mannopyranoside；[(2R,3R,4S,5S,6R)-3-hydroxy-4,5-bis(phenylmethoxy)-6-phenylsulfanyloxan-2-yl]methyl acetate
• CAS: 1421832-62-3
• 化学式: C₂₈H₃₀O₆S
• 分子量: 494.609
• InChiKey: IKCZLXOUHSBRSD-URYJJRPLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  35
• 可旋转键数：
  11
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  99.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  phenylthio 4-O-acetyl-2,3-di-O-benzyl-6-O-trityl-α-D-mannopyranoside 在 copper(II) sulfate 作用下， 以 苯 为溶剂， 以55%的产率得到phenylthio 6-O-acetyl-2,3-di-O-benzyl-α-D-mannopyranoside
  参考文献：
  名称：

  Influence of O6 in Mannosylations Using Benzylidene Protected Donors: Stereoelectronic or Conformational Effects?

  摘要：

  The stereoselective synthesis of beta-mannosides and the underlying reaction mechanism have been thoroughly studied, and especially the benzylidene-protected mannosides have gained a lot of attention since the corresponding mannosyl triflates often give excellent selectivity. The hypothesis for the enhanced stereoselectivity has been that the benzylidene locks the molecule in a less reactive conformation with the O6 trans to the ring oxygen (O5), which would stabilize the formed alpha-triflate and subsequent give beta-selectivity. In this work, the hypothesis is challenged by using the carbon analogue (C7) of the benzylidene-protected mannosyl donor, which is investigated in terms of diastereoselectivity and reactivity and by low-temperature NMR In terms of diastereoselectivity, the C-7-analogue behaves similarly to the benzylidene-protected donor, but its low-temperature NMR reveals the formation of several reactive intermediate. One of the intermediates was found to be the beta-oxosulfonium ion. The reactivity of the donor was found to be in between that of the "torsional" disarmed and an armed donor.

  DOI：

  10.1021/jo302455d

文献信息

• A metal free mild and green approach for tandem opening of 4,6-O-benzylidene acetals to their corresponding 6-O-acetyl derivatives: Application in the synthesis of a trisaccharide using one-pot glycosylation reactions
  作者：Mana Mohan Mukherjee、Nabamita Basu、Shantanu Nandi、Rina Ghosh

  DOI：10.1016/j.carres.2019.03.002

  日期：2019.4

  An efficient and high yielding reaction for tandem opening of 4,6-O-benzylidene derivatives (gluco, galacto, manno, 2-phthalimido-2-deoxy glucosides) to their corresponding 6-O-acetyl derivatives has been established under metal free condition using 60% solution of aqueous acetic acid (v/v). The reaction is equally pertinent for large scale synthesis and also for disaccharide glycosides. Its application

  在无金属条件下，已经建立了一种高效，高产率的串联打开4,6-O-亚苄基衍生物（葡萄糖，半乳糖，甘露糖，2-邻苯二甲酰亚胺基-2-脱氧葡萄糖苷）为其相应的6-O-乙酰基衍生物的反应。使用60％的醋酸水溶液（v / v）。该反应对于大规模合成以及对二糖苷而言同样重要。还已经描述了其在构建用于利用一锅糖基化反应合成与铜绿假单胞菌有关的三糖部分的结构单元中的应用。