4-O-Acetyl-3-O-tert-butyldimethylsilyl-6-O-tosyl-D-glucal | 129693-97-6

• 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: 4-O-Acetyl-3-O-tert-butyldimethylsilyl-6-O-tosyl-D-glucal
• 英文别名: [(2R,3R,4R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[(4-methylphenyl)sulfonyloxymethyl]-3,4-dihydro-2H-pyran-3-yl] acetate
• CAS: 129693-97-6
• 化学式: C₂₁H₃₂O₇SSi
• 分子量: 456.632
• InChiKey: GZDNVDZEAGANIJ-AQNXPRMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.93
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  96.5
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  4-O-Acetyl-3-O-tert-butyldimethylsilyl-6-O-tosyl-D-glucal 在 Raney-Ni W-2 N-碘代丁二酰亚胺 、 偶氮二异丁腈 、 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 三苯基氢化锡 、 triethylamine tris(hydrogen fluoride) 、 sodium iodide 作用下， 以 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  Synthesis of C-D-E trisaccharide precursors of olivomycin A.

  摘要：

  Syntheses of functionalized C-D-E trisaccharide precursors (16, 5) of olivomycin A are reported. A stereoselective C-D beta-glycosidation was accomplished by employing 2-deoxy-2-(phenylthio)-alpha-glucotrichloro-acetimidate 8. The alpha-D-E glycosidic linkage was introduced by using 2-deoxy-2-iodo-alpha-glycosyl acetate donor 14 as the glycosyl transfer agent.

  DOI：

  10.1021/jo00044a010
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 咪唑 、 4-二甲氨基吡啶 作用下， 以 吡啶 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 4-O-Acetyl-3-O-tert-butyldimethylsilyl-6-O-tosyl-D-glucal
  参考文献：
  名称：

  尝试3-O-叔丁基二甲基甲硅烷基-6-O-甲苯磺酰基-d-葡糖基进行苄基化时，甲硅烷基迁移并形成脱水衍生物

  摘要：

  合成d'anhydro-3,6叔丁基二甲基甲硅烷基-4葡糖醛和d'O-甲苯磺酰基-6葡糖醛及丁基氯二甲基硅烷

  DOI：

  10.1016/0008-6215(90)84158-q

文献信息

• Iodoacetoxylation of Glycals Using Cerium(IV) Ammonium Nitrate, Sodium Iodide, and Acetic Acid:  Stereoselective Synthesis of 2-Deoxy-2-iodo-α-mannopyranosyl Acetates
  作者：William R. Roush、Sridhar Narayan、Chad E. Bennett、Karin Briner

  DOI：10.1021/ol990815g

  日期：1999.9.1

  [formula: see text] The reactions of glycals with ceric(IV) ammonium nitrate and sodium iodide in the presence of acetic acid provides 2-deoxy-2-iodo-alpha-mannopyranosyl acetates with good stereoselectivity. In the majority of the cases examined, the selectivity was considerably better than that from reactions using N-iodosuccinimide and HOAc.

  乙酸与硝酸铈（IV）铵盐和碘化钠在乙酸存在下的反应，可得到具有良好立体选择性的2-脱氧-2-碘-α-甘露吡喃糖基乙酸酯。在大多数检查的情况下，其选择性明显优于使用N-碘代琥珀酰亚胺和HOAc的反应。
• Stereoselective Synthesis of 2-Deoxy-β-glycosides From Glycal Precursors. 1. Stereochemistry of the Reactions of ?-Glucal Derivatives with Phenylsulfenyl Chloride and Phenylselenenyl Chloride
  作者：W Roush*

  DOI：10.1016/s0040-4020(97)00571-1

  日期：1997.6.30
• Studies on the Synthesis of Aureolic Acid Antibiotics: Highly Stereoselective Synthesis of Aryl 2-Deoxy-.beta.-glycosides via the Mitsunobu Reaction and Synthesis of the Olivomycin A-B Disaccharide
  作者：William R. Roush、Xiao-Fa Lin

  DOI：10.1021/ja00113a013

  日期：1995.3

  The Mitsunobu reaction of phenols and 1,2-cis-2-thiophenyl-alpha-D-glycopyranoses or 1,2-cis-2-selenophenyl-alpha-D-glycopyranoses is a very effective method for the highly stereoselective synthesis of aryl 2-deoxy-beta-D-glycosides. The equatorial 2-thiophenyl or 2-selenophenyl- substituents are easily removed by Bu(3)SnH reduction following the glycosidation reaction to provide the aryl 2-deoxy-beta-D-glycosides in good to excellent yield. The aryl beta-D-glycosides are obtained with 6.5:1 selectivity in the least selective case(Table 1) and up to >20:1 selectivity in others. The reaction appears to be S-N(2)-like in character (see 30), in that the beta:alpha reaction stereoselectivity correlates well with the alpha:beta anomeric composition of the pyranose starting material. The equatorial 2-thiophenyl or 2-selenophenyl substituents play an important role by increasing the alpha:beta anomer ratio of the pyranose starting materials. The reactions do not appear to proceed by way of free oxonium ions such as 17, since several reactions in which 17 was deliberately generated (e.g., TMS-OTf promoted reactions of glycosyl acetate 14, BF3 . Et(2)O catalyzed reactions of imidate 15) gave at best 1:1 mixtures of alpha- and beta-glycosides, and in several cases gave alpha-glycosides with >10:1 selectivity. These data also rule out the involvement of episulfonium ion 18 as a kinetically significant intermediate in reactions that proceed by way of oxonium ion 17. A short and highly effective synthesis of reducing disaccharide 53 from D-fucal was developed. This functionalized disaccharide readily undergoes Mitsunobu glycosidation with 2-naphthol, providing the model naphthyl A-B disaccharide 5 with 11:1 beta,alpha:alpha,alpha selectivity. Finally, olivin precursor 63 has also been glycosylated with 53, providing the advanced synthetic intermediate 6 with excellent diastereoselectivity.
• A highly stereoselective synthesis of aryl 2-deoxy-.beta.-glycosides via the Mitsunobu reaction
  作者：William R. Roush、Xiao Fa Lin

  DOI：10.1021/jo00020a003

  日期：1991.9

  A highly stereoselective (6.5- > 20:1) synthesis of aryl 2-deoxy-beta-D-glycosides is described. This method involves the Mitsunobu coupling of phenols and 2-alpha-(thiophenyl)- or 2-alpha-(selenophenyl)-alpha-D-pyranoses 3-6, 18, and 19 followed by Bu3SnH reduction of the PhS- and PhSe-groups.
• CRICH, DAVID;RITCHIE, TIMOTHY J., CARBOHYDR. RES., 197,(1990) C. 324-326
  作者：CRICH, DAVID、RITCHIE, TIMOTHY J.

  DOI：——

  日期：——