Acetic acid (2S,3S,4S)-3-acetoxy-6-(diethoxy-thiophosphorylsulfanyl)-2-methyl-tetrahydro-pyran-4-yl ester | 153223-05-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid (2S,3S,4S)-3-acetoxy-6-(diethoxy-thiophosphorylsulfanyl)-2-methyl-tetrahydro-pyran-4-yl ester
• CAS: 153223-05-3
• 化学式: C₁₄H₂₅O₇PS₂
• 分子量: 400.454
• InChiKey: KUCJBNRQUIQWGJ-CPZNGJIXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.02
• 重原子数：
  24.0
• 可旋转键数：
  8.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  80.29
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  磷酸二苄酯 、 Acetic acid (2S,3S,4S)-3-acetoxy-6-(diethoxy-thiophosphorylsulfanyl)-2-methyl-tetrahydro-pyran-4-yl ester 在 molecular sieve 、 iodonium(di-γ-collidine) perchlorate 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以7%的产率得到dibenzyl (3,4-di-O-acetyl-2,6-dideoxy-α-L-arabino-hexopyranosyl) phosphate
  参考文献：
  名称：

  Synthetic approaches to 2-deoxyglycosyl phosphates

  摘要：

  By the use of the N-iodosuccinimide (NIS)-procedure, various glycals could be converted into 2-deoxy-2-iodoglycosyl phosphates. Treatment of glycals 1 and 7 with NIS and dibenzyl phosphate gave the corresponding alpha-1,2-trans-diaxial 2-deoxy-2-iodoglycosyl phosphates 2 and 8 as the main products. The beta-1,2-trans-diequatorial compounds 3 and 9 were isolated as by-products. Analogous reaction of glycals 4 and 10 gave the corresponding 2-deoxy-2-iodoglycosyl phosphates 5, 6, 11, and 12 as crude products, which were characterized by H-1 NMR spectroscopy. Classical phosphorylation of 2-deoxyglycosyl chlorides 14 and 16 with silver dibenzyl phosphate gave the corresponding dibenzyl 2-deoxy-alpha-glycosyl phosphates 15 and 17. Alternatively, glycosylation of tri-O-acetyl-D-glucal (1) using dibenzyl phosphate and triphenylphosphine hydrobromide afforded 15 in lower yield. The application of S-(2-deoxyglycosyl) phosphorodithioates as glycosyl donors provided the most convenient way to dibenzyl 2-deoxyglycosyl phosphates. The alpha-glycosyl phosphates 15, 20, and 22 could be synthesized by reaction of the 2-deoxyglycosyl dithiophosphates 18, 19, and 21 with dibenzyl phosphate and activation by iodonium di-sym-collidine perchlorate. Similary, the 2,6-dideoxyglycosyl dithiophosphates 23 and 25 gave the 2,6-dideoxy phosphates 24 and 26; however, the isolation of these labile compounds could not be effected.

  DOI：

  10.1016/0008-6215(93)84031-z
• 作为产物：
  描述：

  二硫代磷酸二乙酯 、 3,4-二-O-乙酰-1,5-酐-2,6-双脱氧-L-阿拉伯-己-1-糖醇 以 苯 为溶剂， 反应 24.0h， 生成 Acetic acid (2S,3S,4S)-3-acetoxy-6-(diethoxy-thiophosphorylsulfanyl)-2-methyl-tetrahydro-pyran-4-yl ester
  参考文献：
  名称：

  Convenient Iodonium-Promoted Stereoselective Synthesis of 2-Deoxy-α-glycosides by Use ofS-(2-Deoxyglycosyl) Phosphorodithioates as Donors

  摘要：

  S-(2-脱氧糖基)O,O-二乙基二硫代磷酸酯很容易从糖醛中获得，是在 N-碘代琥珀酰亚胺或双(2,4,6-三甲基吡啶)高氯酸碘鎓等促进剂存在下进行糖基化的方便前体。在一系列的转化中，α- 和 β-糖基供体都立体选择性地连接到受体糖分子 [1,2: 3,4-二-O-异丙叉-α-D-吡喃半乳糖 (1)，苄基 3- O-苄基-2,6-二脱氧-β-L-核糖-吡喃己糖苷 (2) 或苄基 4-O-苄基-2,6-二脱氧-β-L-核糖-吡喃糖苷 (3)] 在主要和次要位置反应时间短且产率普遍令人信服。

  DOI：

  10.1055/s-1992-26321