ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside | 864851-93-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
• 英文别名: [(2R,3R,6S)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-ethoxy-3,6-dihydro-2H-pyran-3-yl] methyl carbonate
• CAS: 864851-93-4
• 化学式: C₁₆H₃₀O₆Si
• 分子量: 346.496
• InChiKey: HMKZBMFEKXQADF-MCIONIFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  23
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside 在 tris(dibenzylideneacetone)dipalladium (0) 、 叠氮基三甲基硅烷 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 ethyl 4-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-threo-hex-2-enopyranoside 、 ethyl 2-azido-6-O-(tert-butyldimethylsilyl)-2,3,4-trideoxy-α-D-threo-hex-3-enopyranoside
  参考文献：
  名称：

  Stereocontrolled palladium(0)-catalyzed preparation of unsaturated azidosugars: an easy access to 2- and 4-aminoglycosides

  摘要：

  The palladium-catalyzed substitution of alkyl 4,6-di-O-acetyl-alpha-D-erythro-hex-2-eno-pyranosides using NaN3 as the nucleophile gave predominantly the corresponding alkyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-2-enopyranosides in the presence of Pd(PPh3)(4). However, alkyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosi des were obtained as the major products using Pd(PPh3)4 as the catalyst in the presence of dppb as the added ligand. Conversely, alkyl 6-O-(tert-butyidimethylsilyl)-4-0-methoxycarbonyl-2,3-dideoxy-alpha-D-hex-2-enopyranosides gave exclusively alkyl 4-azido-6-O-(tert-butyldimethylsilyi)-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosides in the presence of Pd-2(dba)(3)/PPh3 as the catalyst and Me3SiN3 as the nucleophile. The bis-hydroxylation followed by hydrogenation of ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside afforded the corresponding 4-amino-alpha-D-mannopyranoside, when propyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-3-enopyranoside gave the 2-amino-alpha-D-altropyranoside under the same conditions. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.06.041
• 作为产物：
  描述：

  乙基 2,3-二脱氧-D-己-2-烯基吡喃糖苷 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 氯乙酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 50.0h， 生成 ethyl 6-O-(tert-butyldimethylsilyl)-4-O-methoxycarbonyl-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  Stereocontrolled palladium(0)-catalyzed preparation of unsaturated azidosugars: an easy access to 2- and 4-aminoglycosides

  摘要：

  The palladium-catalyzed substitution of alkyl 4,6-di-O-acetyl-alpha-D-erythro-hex-2-eno-pyranosides using NaN3 as the nucleophile gave predominantly the corresponding alkyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-2-enopyranosides in the presence of Pd(PPh3)(4). However, alkyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosi des were obtained as the major products using Pd(PPh3)4 as the catalyst in the presence of dppb as the added ligand. Conversely, alkyl 6-O-(tert-butyidimethylsilyl)-4-0-methoxycarbonyl-2,3-dideoxy-alpha-D-hex-2-enopyranosides gave exclusively alkyl 4-azido-6-O-(tert-butyldimethylsilyi)-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosides in the presence of Pd-2(dba)(3)/PPh3 as the catalyst and Me3SiN3 as the nucleophile. The bis-hydroxylation followed by hydrogenation of ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside afforded the corresponding 4-amino-alpha-D-mannopyranoside, when propyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-3-enopyranoside gave the 2-amino-alpha-D-altropyranoside under the same conditions. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.06.041