(2R,4aR,6R,7S,8S,8aR)-8-Allyloxy-7-benzyloxy-6-ethylsulfanyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine | 319922-04-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,4aR,6R,7S,8S,8aR)-8-Allyloxy-7-benzyloxy-6-ethylsulfanyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
• CAS: 319922-04-8
• 化学式: C₂₅H₃₀O₅S
• 分子量: 442.576
• InChiKey: LABRSGYDXODRRZ-AQXIMQTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  31.0
• 可旋转键数：
  9.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  46.15
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2R,4aR,6R,7S,8S,8aR)-8-Allyloxy-7-benzyloxy-6-ethylsulfanyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到(2R,4aR,6R,7S,8S,8aR)-8-Allyloxy-7-benzyloxy-6-ethanesulfinyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  Can preferential β-mannopyranoside formation with 4,6-O-benzylidene protected mannopyranosyl sulfoxides be reached with trichloroacetimidates?

  摘要：

  Studies with 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-alpha -D-mannopyranosyl sulfoxide (3d) and the corresponding trichloroacetimidate (4) as glycosyl donors and various accepters (A-F) led under similar reaction conditions to similar glycosylation results, i.e. mainly or exclusively the p-anomers of glycosides 5dA-5dF could be obtained. Thus, the versatile building block 5dA for N-glycan synthesis is readily available. For the activation of the sulfoxide leaving group, one equivalent of Tf2O and two equivalents of DTBMP are required, whereas for trichloroacetimidate activation catalytic amounts of TMSOTf are sufficient; hence, the trichloroacetimidate based procedure is very convenient. Various parameters were modified in the reaction of 4 with A (catalyst concentration, configuration of 4, size of the 2-O-protective group, solvent), thus, a proposal for the reaction course was derived. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01497-0
• 作为产物：
  描述：

  ethyl 1-thio-α-D-mannopyranoside 在 sodium hydride 、 二正丁基氧化锡 、 对甲苯磺酸 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 生成 (2R,4aR,6R,7S,8S,8aR)-8-Allyloxy-7-benzyloxy-6-ethylsulfanyl-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxine
  参考文献：
  名称：

  Can preferential β-mannopyranoside formation with 4,6-O-benzylidene protected mannopyranosyl sulfoxides be reached with trichloroacetimidates?

  摘要：

  Studies with 3-O-allyl-2-O-benzyl-4,6-O-benzylidene-alpha -D-mannopyranosyl sulfoxide (3d) and the corresponding trichloroacetimidate (4) as glycosyl donors and various accepters (A-F) led under similar reaction conditions to similar glycosylation results, i.e. mainly or exclusively the p-anomers of glycosides 5dA-5dF could be obtained. Thus, the versatile building block 5dA for N-glycan synthesis is readily available. For the activation of the sulfoxide leaving group, one equivalent of Tf2O and two equivalents of DTBMP are required, whereas for trichloroacetimidate activation catalytic amounts of TMSOTf are sufficient; hence, the trichloroacetimidate based procedure is very convenient. Various parameters were modified in the reaction of 4 with A (catalyst concentration, configuration of 4, size of the 2-O-protective group, solvent), thus, a proposal for the reaction course was derived. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)01497-0

文献信息

• Synthesis of a pentasaccharide repeating unit corresponding to the cell wall O-antigen of Escherichia coli O59 using iterative glycosylations in one pot
  作者：Anshupriya Si、Anup Kumar Misra

  DOI：10.1016/j.tet.2016.06.025

  日期：2016.7

  Synthesis of a pentasaccharide repeating unit corresponding to the cell wall O-antigen of Escherichia coli O59 has been achieved by orthogonal glycosylation and two iterative glycosylations in one pot. Synthesis of a β-d-mannosidic linkage present in the molecule has been successfully achieved with satisfactory yield by the activation of thioglycoside with a combination of 1-benzenesulfinyl piperidine

  通过在一个罐中进行正交糖基化和两次迭代糖基化，已经合成了对应于大肠杆菌O59细胞壁O抗原的五糖重复单元。通过将硫代糖苷与1-苯亚磺酰基哌啶（BSP）和三氟甲磺酸酐（Tf 2 O）结合活化，可以令人满意的产率成功地完成了分子中存在的β- d-甘露糖苷键的合成。从α- d以中等收率获得了α- d-氨基葡萄糖氨基部分-甘露糖基部分通过叠氮分解C-2羟基进行构型反转。TEMPO介导的伯羟基的选择性氧化已在合成策略的后期进行。