2,3-dideoxy-1-O-oxidanyl-4,6-di-O-pivaloyl-β-D-erythro-hex-2-enopyranose

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: 2,3-dideoxy-1-O-oxidanyl-4,6-di-O-pivaloyl-β-D-erythro-hex-2-enopyranose
• 英文别名: [(2R,3S,6S)-3-(2,2-dimethylpropanoyloxy)-6-hydroperoxy-3,6-dihydro-2H-pyran-2-yl]methyl 2,2-dimethylpropanoate
• 化学式: C₁₆H₂₆O₇
• 分子量: 330.378
• InChiKey: BOJPAUYEAVMMEV-TUAOUCFPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  91.3
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  ethyl 4,6-di-O-acetyl-2,3-dideoxy-α-D-erythrohex-2-enopyranoside 在 吡啶 、 甲醇 、 硫酸 、 双氧水 、 potassium carbonate 、 三乙胺 作用下， 以 1,4-二氧六环 、 水 为溶剂， 反应 114.0h， 生成 2,3-dideoxy-1-O-oxidanyl-4,6-di-O-pivaloyl-β-D-erythro-hex-2-enopyranose
  参考文献：
  名称：

  The design and synthesis of novel anomeric hydroperoxides: influence of the carbohydrate residue in the enantioselective epoxidation of quinones

  摘要：

  We present a study of the base (DBU)-catalysed epoxidation of a number of important naturally occurring quinones using a series of pyranose-derived anomeric hydroperoxides. The absolute (viz. D or L) stereochemistry of the carbohydrate, electronic nature of the 6-substituent and ring substitution are all important variables. both for the formation of the hydroperoxide and its reactivity. Reactions studied were the epoxidation of a precursor of the natural antibiotic. alisamycin and a series of naphthoquinones related to Vitamin K. In the best case, an ee of 82% was obtained; either product enantiomer is accesssible according to the absolute stereochemistry of the carbohydrate. Finally, a molecular modelling study of the reaction is reported, concluding chat the reactions are under kinetic control and that the observed ees cannot be explained by considering transition states, that involve only the quinone and peroxide anion. It seems likely that the DBU molecule may., play a key role in the transition state. (C) 2004 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2004.11.015

文献信息

• Dwyer, Catherine L.; Gill, Christopher D.; Ichihara, Osamu, Synlett, 2000, # 5, p. 704 - 706
  作者：Dwyer, Catherine L.、Gill, Christopher D.、Ichihara, Osamu、Taylor, Richard J. K.

  DOI：——

  日期：——
• The design and synthesis of novel anomeric hydroperoxides: influence of the carbohydrate residue in the enantioselective epoxidation of quinones
  作者：Abass Bundu、Neil G. Berry、Christopher D. Gill、Catherine L. Dwyer、Andrew V. Stachulski、Richard J.K. Taylor、John Whittall

  DOI：10.1016/j.tetasy.2004.11.015

  日期：2005.1

  We present a study of the base (DBU)-catalysed epoxidation of a number of important naturally occurring quinones using a series of pyranose-derived anomeric hydroperoxides. The absolute (viz. D or L) stereochemistry of the carbohydrate, electronic nature of the 6-substituent and ring substitution are all important variables. both for the formation of the hydroperoxide and its reactivity. Reactions studied were the epoxidation of a precursor of the natural antibiotic. alisamycin and a series of naphthoquinones related to Vitamin K. In the best case, an ee of 82% was obtained; either product enantiomer is accesssible according to the absolute stereochemistry of the carbohydrate. Finally, a molecular modelling study of the reaction is reported, concluding chat the reactions are under kinetic control and that the observed ees cannot be explained by considering transition states, that involve only the quinone and peroxide anion. It seems likely that the DBU molecule may., play a key role in the transition state. (C) 2004 Elsevier Ltd. All rights reserved.