2,4-di-O-benzoyl-3-O-bromoacetyl-α-L-rhamnopyranosyl chloride | 142967-72-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,4-di-O-benzoyl-3-O-bromoacetyl-α-L-rhamnopyranosyl chloride
• 英文别名: [(2S,3S,4R,5R,6S)-5-benzoyloxy-4-(2-bromoacetyl)oxy-6-chloro-2-methyloxan-3-yl] benzoate
• CAS: 142967-72-4
• 化学式: C₂₂H₂₀BrClO₇
• 分子量: 511.754
• InChiKey: CNHISTCOPLPFKC-NIOVVQFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  31.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  88.13
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  2,4-di-O-benzoyl-3-O-bromoacetyl-α-L-rhamnopyranosyl chloride 在 palladium on activated charcoal 2,4,6-三甲基吡啶 、 氢气 、 silver trifluoromethanesulfonate 、 silver perchlorate 、 硫脲 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 2.5h， 生成 methyl O-(2-acetamido-2-deoxy-3,4,6-tri-O-acetyl-α-D-glucopyranosyl)-(1-3)-O-(2,4-di-O-benzoyl-α-L-rhamnopyranosyl)-(1-3)-2,4-di-O-benzoyl-α-L-rhamnopyranoside
  参考文献：
  名称：

  Stereoselective syntheses of a di-, tri-, and tetra-saccharide fragment of shigella dysenteriae type 1 O-antigen using 3,4,6-tri-O-acetyl-2-azido-2-deoxy-α-d-glucopyranosyl chloride as a glycosyl donor

  摘要：

  Methyl 2,4-di-O-benzoyl-alpha-L-rhamnopyranoside (1) furnished a crystalline 3-0-bromoacetyl derivative that was treated with the dichloromethyl methyl ether-ZnCl2 reagent to give 2,4-di-O-benzoyl-3-O-bromoacetyl-alpha-L-rhamnopyranosyl chloride (3). Compounds 1 and 3 were condensed under the conditions of base-deficient, silver trifluoromethanesulfonate-mediated glycosylation to give a fully protected rhamnobioside, which on O-debromoacetylation afforded the disaccharide nucleophile 10. Similar condensation of 3 with methyl 3-O-benzoyl-4,6-O-benzylidene-alpha-D-galactopyranoside, followed by O-debromoacetylation and condensation of the thus formed methyl O-(2,4-di-O-benzoyl-alpha-L-rhamopyranosyl)-(1 --> 2)-4,6-O-benzylidene-3-O-benzoyl-alpha-D-galactopyranoside again with 3, gave the trisaccharide glycoside. Subsequent O-debromoacetylation gave 17, having only HO-3(3) unsubstituted. Silver perchlorate-mediated glycosylations of 1, 10, and 17 with 3.4.6-tri-O-acetyl-2-azido-2-deoxy-alpha-D-glucopyranosyl chloride afforded, with high alpha stereoselectivity, protected di-, tri-, and tetra-saccharide glycosides. Subsequent hydrogenation, followed by N-acetylation and O-deacylation, afforded three oligosaccharide glycosides having nonreducing terminal 2-acetamido-2-deoxy-alpha-D-glucopyranosyl residues and comprising successively larger portions of the repeating unit of Shigella dysenteriae type 1 O-antigen.

  DOI：

  10.1016/s0008-6215(00)90483-x
• 作为产物：
  描述：

  methyl 4-O-benzoyl-2,3-O-isopropylidene-α-L-rhamnopyranoside 在 吡啶 、 zinc chloride diethyl ether 、 1,1-二氯甲醚 、 硫酸 、 D(+)-10-樟脑磺酸 、 三氟乙酸 作用下， 以 甲醇 、 二氯甲烷 、 乙腈 为溶剂， 反应 9.72h， 生成 2,4-di-O-benzoyl-3-O-bromoacetyl-α-L-rhamnopyranosyl chloride
  参考文献：
  名称：

  痢疾志贺氏菌1型O特异性多糖的八糖片段的融合合成。

  摘要：

  描述了线性八糖甲基糖苷α-L-Rhap-（1-> 2）-alpha-D-Gal p-（1> 3）-alpha-Glc p NAc-（ 1-> 3）-al pha-L-Rha p-（1-> 3）-alpha-L-Rha p-（1-> 2）-alpha-D-Gal p-（1-> 3）-α-D-Glcp NAc-（1→3）-α-L-Rhap-OMe（11），其对应于痢疾志贺氏菌1型的O特异性多糖的两个连续重复单元。

  DOI：

  10.1016/0008-6215(94)84079-2

文献信息

• Immunogens related to the synthetic tetrasaccharide side chain of the Bacillus anthracis exosporium
  作者：Rina Saksena、Roberto Adamo、Pavol Kováč

  DOI：10.1016/j.bmc.2007.03.057

  日期：2007.6

  The known methyl 2-O-acetyl-3,4-di-O-benzyl-1-thio-alpha-L-rhamnopyranoside (3) was converted to the corresponding 5-methoxycarbonylpentyl glycoside 4 which was deacetylated. The product 5 was used as the initial glycosyl acceptor to construct two trirhamnoside glycosyl acceptors having HO-3(III) flanked by either benzoyl or benzyl groups, compounds 10 and 29, respectively [fully protected, except HO-3(III)

  将已知的甲基2-O-乙酰基-3,4-二-O-苄基-1-硫代-α-L-鼠李糖吡喃糖苷（3）转化为相应的5-甲氧基羰基戊基糖苷4，其被去乙酰化。产物5用作起始的糖基受体，以构建两个侧接苯甲酰基或苄基的HO-3（III）的三鼠李糖苷糖基受体，分别是化合物10和29 [除HO-3（III）外，均得到充分保护，α -L-Rha-（1-> 3）-alpha-L-Rha-（1-> 2）-alpha-L-Rha-1-O-（CH2）5COOCH3]。当将它们用乙基4-叠氮基-3-O-苄基-4,6-二脱氧-2-O-溴乙酰基-1-硫代β-D-吡喃葡萄糖苷糖基化时（18），只有苄基化的糖基受体29给出了良好的收率。所需的四糖30。α和β连接的产物，以及相应的原酸酯23，当用带有2-O-溴乙酰基保护基的糖基供体进行10个糖基化时，几乎以相等的量形成α-β。在O-2为30时脱保护，然后进一步使分子官能化并整体脱保护，