4-O-acetyl-3-O-(tert-butyldimethylsilyl)-2-deoxy-2-thiophenyl-6-O-p-toluenesulfonyl-1-trichloroacetimido-α-D-glucopyranose | 142865-94-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-2-deoxy-2-thiophenyl-6-O-p-toluenesulfonyl-1-trichloroacetimido-α-D-glucopyranose
• 英文别名: 1-O-(4-O-acetyl-3-O-tert-butyldimethylsilyl-2-thiophenyl-6-O-tosyl-α-D-glycopyranosyl)trichloroacetimidate；PhS(-2d)[TBDMS(-3)][Tos(-6)]Glc4Ac(a)-O-C(NH)CCl3；[(2R,3R,4S,5R,6R)-4-[tert-butyl(dimethyl)silyl]oxy-2-[(4-methylphenyl)sulfonyloxymethyl]-5-phenylsulfanyl-6-(2,2,2-trichloroethanimidoyl)oxyoxan-3-yl] acetate
• CAS: 142865-94-9
• 化学式: C₂₉H₃₈Cl₃NO₈S₂Si
• 分子量: 727.199
• InChiKey: NZDGPBDYHHWDNW-WSGIOKLISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.27
• 重原子数：
  44
• 可旋转键数：
  13
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  155
• 氢给体数：
  1
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  4-O-acetyl-3-O-(tert-butyldimethylsilyl)-2-deoxy-2-thiophenyl-6-O-p-toluenesulfonyl-1-trichloroacetimido-α-D-glucopyranose 在 三氟甲磺酸三甲基硅酯 、 4 A molecular sieve 、 triethylamine tris(hydrogen fluoride) 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.08h， 生成 Acetic acid (2R,3S,4S,5R,6R)-6-[(2R,3S,4R,6S)-3-acetoxy-2-(toluene-4-sulfonyloxymethyl)-6-(2-trimethylsilanyl-ethoxy)-tetrahydro-pyran-4-yloxy]-4-hydroxy-5-phenylsulfanyl-2-(toluene-4-sulfonyloxymethyl)-tetrahydro-pyran-3-yl ester
  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：

  4-O-Acetyl-3-O-tert-butyldimethylsilyl-6-O-tosyl-D-glucal 在 水 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 silver carbonate 作用下， 生成 4-O-acetyl-3-O-(tert-butyldimethylsilyl)-2-deoxy-2-thiophenyl-6-O-p-toluenesulfonyl-1-trichloroacetimido-α-D-glucopyranose
  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

文献信息

• Total Synthesis of the Postulated Structure of Fulicineroside
  作者：Ruben Bartholomäus、Fabian Dommershausen、Markus Thiele、Narayan S. Karanjule、Klaus Harms、Ulrich Koert

  DOI：10.1002/chem.201204545

  日期：2013.6.3

  A total synthesis of the proposed structures of fulicineroside and its aglycone fulicinerine is reported. The tetrasubstituted dibenzofuran substructure was accessible either through a Pd‐mediated ortho‐metalation or by an Ir‐catalyzed meta‐borylation. The synthesis of the β,β,α‐linked trisaccharide consisting of D‐olivose, L‐rhodinose, and L‐rhamnose was challenged by the unprecedented β‐linked rhodinose

  报道了黄腐苷和其糖苷配基黄嘌呤碱的建议结构的全合成。四取代的二苯并呋喃亚结构可通过Pd介导的原金属化或通过Ir催化的间硼化来获得。由D-寡糖，L-罗丹糖和L-鼠李糖组成的β，β，α-连接的三糖的合成受到前所未有的β-连接的罗丹糖的挑战。Pd催化的4-表位-若丹糖的β-选择性糖基化反应和随后的Mitsunobu倒置可选择性地提供β-连接的L-若丹糖-L鼠李糖二糖。与天然产物和糖苷配基的报道数据进行比较表明，天然产物的结构分配有误。
• Stereoselective synthesis of 2-deoxy-β-glycosides from glycal precursors. 2. Stereochemistry of glycosidation reactions of 2-thiophenyl- and 2-selenophenyl-α-d-gluco-pyranosyl donors
  作者：William R. Roush、David P. Sebesta、Ray A. James

  DOI：10.1016/s0040-4020(97)90395-1

  日期：1997.6

  configurationally stable (at C(2)). The main problem with imidates 11 is that the stereoselectivity of their reactions with alcohols is substrate dependent, with best selectivity for the desired β-glycosides 35 and 42 being obtained with the least sterically hindered alcohols. The fact that the α-glycosides 36 and 43 comprise up to 20–50% of the product in glycosidation reactions of hindered secondary

  我们已经证明了4-O-乙酰基-6-溴-3-O-（叔丁基二甲基甲硅烷基）-2-脱氧-2-硫代苯基-1-三氯乙酰胺基-α-d-吡喃葡萄糖11b是最有效和选择性的供体用于所考察的一系列糖基供体的2-脱氧-β-糖苷的合成。不同于2-硒吩基取代的供体8，其被证明是下标TMS-光学传递函数构型上不稳定的促进糖基化的条件下，从而产生α甘露糖苷14，17和20从β葡糖供体8，2-噻吩基取代的供体9和11似乎是完全配置稳定（在C（2））。酰亚胺的主要问题由图11可知，它们与醇的反应的立体选择性取决于底物，而对所期望的β-糖苷35和42的最佳选择性是由受阻最少的醇获得的。在受阻仲醇的糖基化反应中，α-糖苷36和43最多占产物的20-50％，这一事实支持了以下观点：反应立体选择性不受epi硫离子（47和47'）的中间性支配，而是氧离子46及其构象上的反相异构体46'的取代反应起主要作用。
• Synthesis of naphthyl A–B disaccharides corresponding to olivomycin A and mithramycin
  作者：William R. Roush、Xiao-Fa Lin

  DOI：10.1016/s0040-4039(00)91806-9

  日期：1993.10

  Highly stereoselective syntheses of naphthyl disaccharides 4 and 5, which correspond to the A-B disaccharide units of olivomycin A and mithramycin, are described.
• Studies on the Synthesis of Aureolic Acid Antibiotics:  Acyloin Glycosidation Studies
  作者：William R. Roush、Karin Briner、Brenda S. Kesler、Megan Murphy、Darin J. Gustin

  DOI：10.1021/jo960932e

  日期：1996.1.1