[(2R,3S,4R)-3,4-diacetyloxy-5-azido-6-nitrooxyoxan-2-yl]methyl acetate | 668481-16-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: [(2R,3S,4R)-3,4-diacetyloxy-5-azido-6-nitrooxyoxan-2-yl]methyl acetate
• CAS: 668481-16-1
• 化学式: C₁₂H₁₆N₄O₁₀
• 分子量: 376.28
• InChiKey: ZJRHNHIEORAKEY-GYOGACSVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  26
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  158
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  [(2R,3S,4R)-3,4-diacetyloxy-5-azido-6-nitrooxyoxan-2-yl]methyl acetate 在 sodium 、 对甲苯磺酸 作用下， 以 乙腈 为溶剂， 反应 6.5h， 生成 methyl 2-azido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Synthesis of Two Hyaluronan Trisaccharides

  摘要：

  The synthesis of two hyaluronan trisaccharides, methyl O(beta-D-glucopyranosyluronic acid)-(1,3)-O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-(1,4)-O-beta-D-glucopyranosiduronic acid and methyl O-(2-acetamido-2-deoxy-beta-D-glucopyranosyl)-(1,4)-O-beta-D-glycopyranosyluronic acid)-(1,3)-O-(2-acetamido-2-deoxy-beta-D-glucopyranoside are described. Construction of the target molecules was achieved though a combination of the phenyl sulfoxide and trichloroacetimidate glycosylation methodologies. This is the first report on the synthesis of the beta-methyl derivatives, which represent the smallest fragments that incorporate all the structural features of polymeric hyaluronan.

  DOI：

  10.1021/ol0057075
• 作为产物：
  描述：

  乙酰化葡萄烯糖 在 sodium azide 、 ammonium cerium(IV) nitrate 作用下， 以 乙腈 为溶剂， 生成 [(2R,3S,4R)-3,4-diacetyloxy-5-azido-6-nitrooxyoxan-2-yl]methyl acetate
  参考文献：
  名称：

  Unusual stereoselectivity in sialic acid aldolase-catalyzed aldol condensations: synthesis of both enantiomers of high-carbon monosaccharides

  摘要：

  An inversion of stereoselectivity in aldol condensations catalyzed by sialic acid aldolase (from Escherichia coli, Shinko American Inc.) was observed when L-mannose, 6-deoxy-L-mannose, L-talose, 2-deoxy-L-glucose, 2-deoxy-L-rhamnose, N-acetyl-L-mannosamine, D-gulose, D-arabinose, and 2-azido-2-deoxy-L-mannose were used as acceptor substrates. In all substrates tested, except the last three, a complete inversion of stereoselectivity was observed; i.e., the C-nucleophile of pyruvate attacks the re face of the acceptor carbonyl instead of the si face as in the normal case for the enantiomeric substrates. Examination of the product distribution during the course of enzymatic reactions indicates that the stereoselectivity is thermodynamically controlled in nature; i.e., attack on the re face would take place if the resulting product would be more stable than the one from the si face attack. Both enantiomers of several high-carbon monosaccharides are now accessible via the aldolase reactions. A new practical procedure has also been developed for the preparation of the aldolase products where unreacted pyruvate (usually used in 7-fold excess to drive the reaction) is decomposed with pyruvate decarboxylase to simplify product isolation.

  DOI：

  10.1021/ja00052a008

文献信息

• Investigating Cellular Metabolism of Synthetic Azidosugars with the Staudinger Ligation
  作者：Eliana Saxon、Sarah J. Luchansky、Howard C. Hang、Chong Yu、Sandy C. Lee、Carolyn R. Bertozzi

  DOI：10.1021/ja027748x

  日期：2002.12.1

  derivatives into cell-surface sialosides. A key tool in this study is the Staudinger ligation, a highly selective reaction between modified triarylphosphines and azides that produces an amide-linked product. A preliminary study of the mechanism of this reaction, and refined conditions for its in vivo execution, are reported. The reaction provided a means to label the glycoconjugate-bound azidosugars with

  活细胞上唾液酸的结构可以通过非天然生物合成前体的代谢进行调节。在这里，我们研究了一组叠氮化物功能化甘露糖胺和葡糖胺衍生物向细胞表面唾液酸苷的转化。本研究中的一个关键工具是 Staudinger 连接，这是一种改性三芳基膦和叠氮化物之间的高度选择性反应，可产生酰胺连接的产物。报告了对该反应机制的初步研究，并报告了其体内执行的完善条件。该反应提供了一种用生化探针标记结合糖缀合物的叠氮糖的方法。最后，我们证明细胞表面施陶丁格结扎与代谢引入的酮形成腙是相容的。
• Direct, microwave-assisted substitution of anomeric nitrate-esters
  作者：D. Jamin Keith、Steven D. Townsend

  DOI：10.1016/j.carres.2017.02.005

  日期：2017.4

  1-nitrate-ester modality for alcohol, alkoxy, and azide coupling partners with minimal purification. While direct glycosylation of nitrate esters ultimately proved unsuccessful, we have demonstrated that an anomeric nitrate-ester can be converted directly to a trichloroacetimidate in a short and simple one-pot procedure, bypassing lower yielding two-step sequences.

  在无试剂的条件下，将一系列在C-3，C-4和C-6位置受保护的碳水化合物2-叠氮基-硝酸盐酯进行热水解。该初步结果已扩展为以最少的纯化将1-硝酸酯-酯形式直接交换为醇，烷氧基和叠氮化物偶联伙伴。虽然最终证明硝酸酯的直接糖基化是不成功的，但我们已经证明，可以在短而简单的一锅法中将异头的硝酸酯直接转化为三氯乙酰亚胺酸酯，而绕过了较低的收率两步法。
• First Total Synthesis of Mycothiol and Mycothiol Disulfide
  作者：Sungwon Lee、John P. N. Rosazza

  DOI：10.1021/ol0362008

  日期：2004.2.1

  The first total synthesis of mycothiol and mycothiol disulfide was achieved by linking D-2,3,4,5,6-penta-O-acetyl-myo-inositol, O-(3,4,6-tri-O-acetyl)-2-azido-2-deoxy-alpha,beta-D-glucopyranosyl) trichloroacetimidate, and N,S-diacetyl-L-cysteine and deprotecting peracetylated mycothiol. The first full spectral characterization is reported for underivatized mycothiol. The structure of mycothiol was confirmed by spectral analysis of the known bimane derivative.
• Grundler, Gerhard; Schmidt, Richard R., Liebigs Annalen der Chemie, 1984, # 11, p. 1826 - 1847
  作者：Grundler, Gerhard、Schmidt, Richard R.

  DOI：——

  日期：——
• Kinzy, Willy; Schmidt, Richard R., Liebigs Annalen der Chemie, 1985, # 8, p. 1537 - 1545
  作者：Kinzy, Willy、Schmidt, Richard R.

  DOI：——

  日期：——