[(2R,3S,4R,6R)-3,4-diacetyloxy-6-dimethoxyphosphoryloxan-2-yl]methyl acetate | 175980-43-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: [(2R,3S,4R,6R)-3,4-diacetyloxy-6-dimethoxyphosphoryloxan-2-yl]methyl acetate
• CAS: 175980-43-5
• 化学式: C₁₄H₂₃O₁₀P
• 分子量: 382.304
• InChiKey: MSWBLOJIAQCFBV-SYQHCUMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  25
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  124
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  [(2R,3S,4R,6R)-3,4-diacetyloxy-6-dimethoxyphosphoryloxan-2-yl]methyl acetate 在 三甲基溴硅烷 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 4.0h， 生成 [(2R,4R,5S,6R)-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]phosphonic acid
  参考文献：
  名称：

  Synthesis of 2-deoxy-α- and -β-D-arabino-hexopyranosyl phosphonic acids and related compounds; analogues of early intermediates in the shikimate pathway

  摘要：

  Treatment of 1-O-acetyl-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hexopyranose 18 with trimethyl phosphite in the presence of trimethylsilyl triflate gave a separable mixture of dimethyl (3,4,6-tri-O-benzyl-alpha-D-arabino-hexopyranosyl)phosphonate 19 (35%) and the beta-anomer 20 (60%). The diethyl analogue of compound 20 could be prepared stereoselectively from tributyl (3,4,6-tri-O-benzyl-2-deoxy-beta-D-arabino-hexopyranosyl)stannane 21 and diethyl chlorophosphate.Reaction of 1,3,4,6-tetra-O-acetyl-2-deoxy-D-arabino-hexopykanose 23 with trimethyl phosphite and trimethylsilyl triflate gave dimethyl (3,4,6-tri-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranosyl)phosphonate 25 and the beta-anomer 27 with some alpha-selectivity. Deprotection of compounds 25 and 27 gave the phosphonic acids 11 and 12 respectively. The esters 25 and 27 could be converted into methyl 3,4,6-tri-O-acetyl-2-deoxy-1-(dimethoxyphosphoryl)-beta-D-arabino-hexopyranoside 31 by free-radical bromination followed by methanolysis, and diethyl [3,4,6-tri-O-(tert-butyldiphenylsilyl)-2-deoxy-D -arabino-hex-1-enopyranosyl)phosphonate 33 was prepared by interaction of the 1-lithioglucal with diethyl chlorophosphate.Metallation of stannane 21 and reaction with methyl chloroformate gave methyl 2,6-anhydro-4,5,7-tri-O-benzyl-3-deoxy-D-gluco-heptonate 35 which could be alkylated with tert-butyl bromoacetate to give, after deprotection, 3,7-anhydro-3-carboxy-2,4-dideoxy-D-gluco-octonic acid 14.

  DOI：

  10.1039/p19960000431
• 作为产物：
  描述：

  3,4,6-O-三乙酰基-2-脱氧-D-葡萄糖 、 三甲氧基磷 在 三氟甲磺酸三甲基硅酯 、 sodium hydride 、 三氯乙腈 作用下， 生成 [(2R,3S,4R,6R)-3,4-diacetyloxy-6-dimethoxyphosphoryloxan-2-yl]methyl acetate
  参考文献：
  名称：

  Synthesis of 2-deoxy-α- and -β-D-arabino-hexopyranosyl phosphonic acids and related compounds; analogues of early intermediates in the shikimate pathway

  摘要：

  Treatment of 1-O-acetyl-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hexopyranose 18 with trimethyl phosphite in the presence of trimethylsilyl triflate gave a separable mixture of dimethyl (3,4,6-tri-O-benzyl-alpha-D-arabino-hexopyranosyl)phosphonate 19 (35%) and the beta-anomer 20 (60%). The diethyl analogue of compound 20 could be prepared stereoselectively from tributyl (3,4,6-tri-O-benzyl-2-deoxy-beta-D-arabino-hexopyranosyl)stannane 21 and diethyl chlorophosphate.Reaction of 1,3,4,6-tetra-O-acetyl-2-deoxy-D-arabino-hexopykanose 23 with trimethyl phosphite and trimethylsilyl triflate gave dimethyl (3,4,6-tri-O-acetyl-2-deoxy-alpha-D-arabino-hexopyranosyl)phosphonate 25 and the beta-anomer 27 with some alpha-selectivity. Deprotection of compounds 25 and 27 gave the phosphonic acids 11 and 12 respectively. The esters 25 and 27 could be converted into methyl 3,4,6-tri-O-acetyl-2-deoxy-1-(dimethoxyphosphoryl)-beta-D-arabino-hexopyranoside 31 by free-radical bromination followed by methanolysis, and diethyl [3,4,6-tri-O-(tert-butyldiphenylsilyl)-2-deoxy-D -arabino-hex-1-enopyranosyl)phosphonate 33 was prepared by interaction of the 1-lithioglucal with diethyl chlorophosphate.Metallation of stannane 21 and reaction with methyl chloroformate gave methyl 2,6-anhydro-4,5,7-tri-O-benzyl-3-deoxy-D-gluco-heptonate 35 which could be alkylated with tert-butyl bromoacetate to give, after deprotection, 3,7-anhydro-3-carboxy-2,4-dideoxy-D-gluco-octonic acid 14.

  DOI：

  10.1039/p19960000431