methyl α-D-6-O-t-butyldimethylsilyl-4-O-methanesulphonyl-2,3-dideoxyhex-2-enoerythropyranoside | 405145-65-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl α-D-6-O-t-butyldimethylsilyl-4-O-methanesulphonyl-2,3-dideoxyhex-2-enoerythropyranoside
• CAS: 405145-65-5
• 化学式: C₁₄H₂₈O₆SSi
• 分子量: 352.524
• InChiKey: VTKWRYMYJOKGGL-XQQFMLRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.28
• 重原子数：
  22.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  methyl α-D-6-O-t-butyldimethylsilyl-4-O-methanesulphonyl-2,3-dideoxyhex-2-enoerythropyranoside 在 Amberlite IRA-900 in azide form 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 methyl α-D-4-azido-6-O-t-butyldimethylsilyl-2,3,4-trideoxyhex-2-enotreopyranoside 、 methyl α-D-2-azido-6-O-t-butyldimethylsilyl-2,3,4-trideoxyhex-3-enoglyceropyranoside
  参考文献：
  名称：

  Steric constraints against [3,3]-sigmatropic rearrangement of allylic azides. A convenient approach to β-l-4-aminopent-2-enoglyceropyranosides

  摘要：

  Starting from alkyl alpha -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 13a-c, nucleophilic substitution carried out with polymer-supported azide ion led to regioisomeric mixtures of the azides 14a-c and 15a-c. An analogous result, due to a [3,3]-sigmatropic rearrangement, was observed starting from methyl alpha -D-hex-2-enoerythropyranoside derivatives 6a and 6b. On the contrary, starting from alkyl beta -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 21a-c, azides 22a-c were exclusively obtained. and subsequently converted into the corresponding amino derivatives 23a-c. The behaviour of P-anomers 21a-c was ascribed to steric interactions in the cyclic transition state, as supported by ab initio calculations. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00450-5
• 作为产物：
  描述：

  methyl 2,3-dideoxy-4,6-dihydroxy-α-D-erythro-hex-2-enopyranoside 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 5.0h， 生成 methyl α-D-6-O-t-butyldimethylsilyl-4-O-methanesulphonyl-2,3-dideoxyhex-2-enoerythropyranoside
  参考文献：
  名称：

  Steric constraints against [3,3]-sigmatropic rearrangement of allylic azides. A convenient approach to β-l-4-aminopent-2-enoglyceropyranosides

  摘要：

  Starting from alkyl alpha -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 13a-c, nucleophilic substitution carried out with polymer-supported azide ion led to regioisomeric mixtures of the azides 14a-c and 15a-c. An analogous result, due to a [3,3]-sigmatropic rearrangement, was observed starting from methyl alpha -D-hex-2-enoerythropyranoside derivatives 6a and 6b. On the contrary, starting from alkyl beta -D-4-O-methanesulphonylpent-2-enoglyceropyranosides 21a-c, azides 22a-c were exclusively obtained. and subsequently converted into the corresponding amino derivatives 23a-c. The behaviour of P-anomers 21a-c was ascribed to steric interactions in the cyclic transition state, as supported by ab initio calculations. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00450-5