3,4,6-tri-O-benzyl-2-O-chloroacetyl-α-D-glucopyranosyl bromide | 205693-44-3

• 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: 3,4,6-tri-O-benzyl-2-O-chloroacetyl-α-D-glucopyranosyl bromide
• 英文别名: [(2R,3R,4S,5R,6R)-2-bromo-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl] 2-chloroacetate
• CAS: 205693-44-3
• 化学式: C₂₉H₃₀BrClO₆
• 分子量: 589.911
• InChiKey: XCUQGWJSBBSNLB-RIAYOEEMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  37
• 可旋转键数：
  13
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  3,4,6-tri-O-benzyl-2-O-chloroacetyl-α-D-glucopyranosyl bromide 、 2-benzyloxy-6-{(16R)-[2-O-acetyl-3,4,6-tri-O-benzyl-D-mannonoyloxy]heptadecyl}benzoic acid benzyl ester 在 van Boeckel catalyst 3 A molecular sieve 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以74%的产率得到2-((R)-16-{(2S,3S,4R,5R)-2-Acetoxy-3,4,6-tris-benzyloxy-5-[(2S,3R,4S,5R,6R)-4,5-bis-benzyloxy-6-benzyloxymethyl-3-(2-chloro-acetoxy)-tetrahydro-pyran-2-yloxy]-hexanoyloxy}-heptadecyl)-6-benzyloxy-benzoic acid benzyl ester
  参考文献：
  名称：

  Total Synthesis of Caloporoside

  摘要：

  The first total synthesis of the fungal metabolite caloporoside 1, a strong and selective inhibitor of phospholipase C, is described. Both sugar units of its complex disaccharidic segment were obtained from 3,4,6-tri-O-benzyl-D-glucopyranose 14 as a common building block, with D-gluco-->D-manno inversions as the key strategic elements. This particular substitution reaction occurred readily on the acyclic segment (27-->28), whereas ultrasonication was required to override adverse stereoelectronic effects upon formation of beta-D-mannopyranoside unit 34. The (16R)-hydroxyheptadecylsalicylic acid part of 1 was efficiently prepared by a palladium-catalyzed Suzuki cross coupling reaction of aryltriflate 7 with the 9-alkyl-9-BBN derivative formed from alkene 6 and 9-H-9-BBN.

  DOI：

  10.1021/jo9800098
• 作为产物：
  描述：

  3,4,6-tri-O-benzyl-D-glucopyranose 在 吡啶 、 氢溴酸 作用下， 以 氯仿 、 溶剂黄146 为溶剂， 反应 4.5h， 生成 3,4,6-tri-O-benzyl-2-O-chloroacetyl-α-D-glucopyranosyl bromide
  参考文献：
  名称：

  Total Synthesis of Caloporoside

  摘要：

  The first total synthesis of the fungal metabolite caloporoside 1, a strong and selective inhibitor of phospholipase C, is described. Both sugar units of its complex disaccharidic segment were obtained from 3,4,6-tri-O-benzyl-D-glucopyranose 14 as a common building block, with D-gluco-->D-manno inversions as the key strategic elements. This particular substitution reaction occurred readily on the acyclic segment (27-->28), whereas ultrasonication was required to override adverse stereoelectronic effects upon formation of beta-D-mannopyranoside unit 34. The (16R)-hydroxyheptadecylsalicylic acid part of 1 was efficiently prepared by a palladium-catalyzed Suzuki cross coupling reaction of aryltriflate 7 with the 9-alkyl-9-BBN derivative formed from alkene 6 and 9-H-9-BBN.

  DOI：

  10.1021/jo9800098

文献信息

• Total Synthesis of Caloporoside
  作者：Alois Fürstner、Ingo Konetzki

  DOI：10.1021/jo9800098

  日期：1998.5.1

  The first total synthesis of the fungal metabolite caloporoside 1, a strong and selective inhibitor of phospholipase C, is described. Both sugar units of its complex disaccharidic segment were obtained from 3,4,6-tri-O-benzyl-D-glucopyranose 14 as a common building block, with D-gluco-->D-manno inversions as the key strategic elements. This particular substitution reaction occurred readily on the acyclic segment (27-->28), whereas ultrasonication was required to override adverse stereoelectronic effects upon formation of beta-D-mannopyranoside unit 34. The (16R)-hydroxyheptadecylsalicylic acid part of 1 was efficiently prepared by a palladium-catalyzed Suzuki cross coupling reaction of aryltriflate 7 with the 9-alkyl-9-BBN derivative formed from alkene 6 and 9-H-9-BBN.