ethyl 4,6-di-O-benzoyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside | 56932-85-5

• 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: ethyl 4,6-di-O-benzoyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
• CAS: 56932-85-5
• 化学式: C₂₂H₂₂O₆
• 分子量: 382.413
• InChiKey: LIXSXQOCTWANFJ-AQNXPRMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.39
• 重原子数：
  28.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ethyl 4,6-di-O-benzoyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside 生成 ethyl 2,3-dideoxy-4,6-di-O-p-toluenesulfonyl-α-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  顺式-氨基氧化途径制取氨糖的方法：holacosamine的简单合成

  摘要：

  将已知的D-苏式hex-2-enopyranoside 1a转化为N-甲基烯丙基胺，对其甲基氨基甲酸酯进行亲电诱导的环化反应，得到碘代氨基甲酸乙酯9。证实了后者中H3和H4的顺式关系通过NMR光谱。同时在C2和C6处还原，然后将环状氨基甲酸酯水解。然后氨基被乙酰化而羟基被甲基化。

  DOI：

  10.1016/s0040-4039(01)83000-8
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 生成 ethyl 4,6-di-O-benzoyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  The synthesis of D-asperlin

  摘要：

  已经合成了阿斯柏林的D-对映体。对于这个D-对映体，环氧环的立体化学已被确定为6R，7S。

  DOI：

  10.1139/v87-057

文献信息

• Stereocontrolled routes to <i>cis</i>-hydroxyamino sugars. Part VII. A synthesis of holacosamine
  作者：Michael Georges、D. Mackay、Bert Fraser-Reid

  DOI：10.1139/v84-262

  日期：1984.8.1

  Methyl 4,6-di-O-p-toluenesulfonyl-α-D-threo-hex-2-enopyranoside 4b reacts with methylamine at room temperature to displace the allylic sulfonate only, and the ethyl urethane of the resulting 4-N-methylamino sugar is cyclized with iodonium ion to give the 2-iodo-oxazolidinone, 13. This substance, upon treatment with sodium iodide in acetone, gives the 2,6-diiodide 14a. Deiodination, followed by base hydrolysis, gives the cis-hydroxyamino precursor, which upon N-acetylation and O-methylation affords the previously known holacosaminide 1b.

  甲基4,6-二-O-p-甲苯磺酰基-α-D-左-己-2-烯基吡喃苷4b在室温下与甲胺反应，只置换烯丙基磺酸酯，所得的4-N-甲基氨基糖的乙基脲醚与碘离子环化形成2-碘-噁唑烷酮13。该物质经过在丙酮中与碘化钠处理后，得到2,6-二碘代14a。去碘化后，经碱水解得到顺式-羟胺前体，经N-乙酰化和O-甲基化后得到已知的holacosaminide 1b。
• 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.