ethyl 3-O-allyl-4,6-O-benzylidene-1-thio-α-D-mannopyranoside | 319922-00-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3-O-allyl-4,6-O-benzylidene-1-thio-α-D-mannopyranoside
• 英文别名: (2R,4aR,6R,7S,8R,8aR)-6-ethylsulfanyl-2-phenyl-8-prop-2-enoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 319922-00-4
• 化学式: C₁₈H₂₄O₅S
• 分子量: 352.452
• InChiKey: RKVNNRUITIJCSA-SISKNIMQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  82.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3-O-allyl-4,6-O-benzylidene-1-thio-α-D-mannopyranoside 在 sodium hydride 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 (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：

  1,2,3,4,6-O-五乙酰基-Alpha-甘露糖 在 三氟化硼乙醚 、 sodium methylate 、 二正丁基氧化锡 、 对甲苯磺酸 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 ethyl 3-O-allyl-4,6-O-benzylidene-1-thio-α-D-mannopyranoside
  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 the pentasaccharide related to the repeating unit of the antigen from Shigella dysenteriae type 4 in the form of its methyl ester 2-(trimethylsilyl)ethyl glycoside
  作者：Balaram Mukhopadhyay、Nirmolendu Roy

  DOI：10.1016/s0008-6215(02)00499-8

  日期：2003.3

  alpha-mannopyranosyl units was transformed, via Walden inversion and subsequent deprotection, into the alpha-D-glucosamine-type target compound, namely methyl alpha-L-fucopyranosyl-(1-->3)-2-acetamido-2-deoxy-alpha-D-glucopyranosyl-(1-->3)-2-acetamido-2-deoxy-4-O-(alpha-L-fucopyranosyl)-alpha-D-glucopyranosyl-(1-->4)-[2-(trimethylsilyl)ethyl beta-D-glucopyranosid]uronate which is related to the repeating unit of the

  从D-甘露糖，D-葡萄糖和L-岩藻糖开始，五糖衍生物甲基2,3,4-三-O-苄基-α-L-富铀糖基-（1-> 3）-2-O-乙酰基- 4,6-O-亚苄基-α-D-甘露吡喃糖基-（1-> 3）-2-O-乙酰基-6-O-苄基-4-O-（2,3,4-三-O-苄基合成了-α-L-呋喃核糖基）-α-D-甘露吡喃糖基-（1→4）-[2-（三甲基甲硅烷基）乙基2，3-二-O-苄基-β-D-吡喃葡萄糖苷]尿酸酯。通过Walden倒置和随后的脱保护反应，将具有两个α-甘露聚糖基的该化合物转化为α-D-葡糖胺型目标化合物，即甲基α-L-呋喃果糖基-（1-> 3）-2-乙酰氨基- 2-脱氧-α-D-吡喃葡萄糖基-（1-> 3）-2-乙酰氨基-2-脱氧-4-O-（α-L-呋喃二糖基）-α-D-吡喃葡萄糖基-（1--
• Synthesis of <i>Cryptococcus neoformans</i> Capsular Polysaccharide Structures. IV. Construction of Thioglycoside Donor Blocks and Their Subsequent Assembly
  作者：Mia Alpe、Stefan Oscarson、Pär Svahnberg

  DOI：10.1081/car-120026459

  日期：2003.12.31

  Di‐ and trisaccharide thioglycoside building blocks, ethyl (2,3,4‐tri‐O‐benzyl‐β‐d‐xylopyranosyl)‐(1→2)‐3‐O‐allyl‐4,6‐di‐O‐benzyl‐1‐thio‐α‐d‐mannopyranoside, ethyl (2,3,4‐tri‐O‐benzyl‐β‐d‐xylopyranosyl)‐(1→2)‐6‐O‐acetyl‐3‐O‐allyl‐4‐O‐benzyl‐1‐thio‐α‐d‐mannopyranoside and ethyl (2,3,4‐tri‐O‐benzyl‐β‐d‐xylopyranosyl)‐(1→4)‐[(2,3,4‐tri‐O‐benzyl‐β‐d‐xylopyranosyl)‐(1→2)]‐3‐O‐allyl‐6‐O‐benzyl‐1‐thio‐α‐d‐mannopyranoside

  二糖和三糖硫代糖苷结构单元，乙基（2,3,4-三-O-苄基-β-d-吡喃吡喃糖基）-（1→2）-3-O-烯丙基-4,6-二-O-苄基-1-硫代-α-d-甘露吡喃糖苷，乙基（2,3,4-三-O-苄基-β-d-吡喃并吡喃糖基）-（1→2）-6-O-乙酰基-3-3-O-烯丙基4-O-苄基-1-硫代-α-d-吡喃吡喃糖苷和乙基（2,3,4-三-O-苄基-β-d-吡喃吡喃糖基）-（1→4）-[（2,3,4 -三-O-苄基-β-d-吡喃吡喃糖基）（（1→2）]-3-O-烯丙基-6-O-苄基-1-硫代-α-d-吡喃吡喃糖苷，对应于荚膜中的重复结构新型隐球菌多糖（CPS）是利用三氟甲磺酸银促进的苯并溴木糖与适当保护的甘露糖乙基硫代糖苷之间的偶联而合成的。这些嵌段在甘露糖残基的3位含有一个正交的烯丙基，以允许CPS（1→3）连接的甘露聚糖主链的继续形成。它们具有苄基醚作为持久性保护基，以促进接近乙酰化靶标结
• Synthesis of<i>Cryptococcus neoformans</i>Capsular Polysaccharide Structures. Part V: Construction of Glucuronic Acid‐Containing Thioglycoside Donor Blocks
  作者：Mia Alpe、Stefan Oscarson、Pär Svahnberg

  DOI：10.1081/car-200040114

  日期：2004.12.27

  Glucuronic acid‐containing di‐ and trisaccharide thioglycoside building blocks, ethyl (benzyl 2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranosyluronate)‐(1 → 2)‐3‐O‐allyl‐4,6‐di‐O‐benzyl‐1‐thio‐α‐D‐mannopyranoside, ethyl (benzyl 2,3,4‐tri‐O‐benzyl‐β‐D‐glucopyranosyluronate)‐(1 → 2)‐6‐O‐acetyl‐3‐O‐allyl‐4‐O‐benzyl‐1‐thio‐α‐D‐mannopyranoside and ethyl (2,3,4‐tri‐O‐benzyl‐β‐D‐xylopyranosyl)‐(1 → 4)‐[(benzyl 2,3,4

  含葡萄糖醛酸的二和三糖硫代糖苷结构单元，乙基（苄基2,3,4-三-O-苄基-β - D-吡喃葡萄糖基尿酸）-（1→2）-3-3- O-烯丙基-4,6-二-O-苄基-1-硫代-α - D-甘露吡喃糖苷，乙基（苄基2,3,4-三-O-苄基-β - D-吡喃葡萄糖基尿酸）-（1→2）-6- O-乙酰基3- ø -烯丙基-4- ö苄基-1-硫代α- d -mannopyranoside和乙基（2,3,4-三ø -苄基β- d -xylopyranosyl） - （1→4） - [ （苄基2,3,4-三-O-苄基-β - D-吡喃葡萄糖基尿酸酸酯）-（1→2）]-3-O-烯丙基-6- O-苄基-1-硫代-α - D-甘露吡喃糖苷，对应于新隐球菌荚膜多糖（CPS）中的重复结构，已经合成。这些嵌段在甘露糖残基的3位上包含一个正交的烯丙基，以允许CPS和苄基醚形成（1→3）连接的甘露聚糖主链，作为持久性保
• Can preferential β-mannopyranoside formation with 4,6-O-benzylidene protected mannopyranosyl sulfoxides be reached with trichloroacetimidates?
  作者：Ralf Weingart、Richard R Schmidt

  DOI：10.1016/s0040-4039(00)01497-0

  日期：2000.11

  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.