5,6-bis(O-tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-C-(Z)-(2-thiocyanatoethylidene)-α-D-glucofuranose | 911122-62-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5,6-bis(O-tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-C-(Z)-(2-thiocyanatoethylidene)-α-D-glucofuranose
• 英文别名: [(2Z)-2-[(3aR,5S,6aR)-5-[(1R)-1,2-bis[[tert-butyl(dimethyl)silyl]oxy]ethyl]-2,2-dimethyl-3a,6a-dihydrofuro[2,3-d][1,3]dioxol-6-ylidene]ethyl] thiocyanate
• CAS: 911122-62-8
• 化学式: C₂₄H₄₅NO₅SSi₂
• 分子量: 515.862
• InChiKey: XQJHUXCYIVJUNU-OTLGCGHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.42
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  95.2
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  5,6-bis(O-tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-C-(Z)-(2-thiocyanatoethylidene)-α-D-glucofuranose 以 乙醚 、 邻二甲苯 为溶剂， 反应 6.0h， 生成 5,6-bis(O-tert-butyldimethylsilyl)-3-(N-cyclopentylthiocarboxamido)-3-deoxy-1,2-O-isopropylidene-3-C-vinyl-α-D-glucofuranose
  参考文献：
  名称：

  Creation of quarternary stereocentres via [3,3]-sigmatropic rearrangement of allylic thiocyanates. A synthetic approach to (+)-myriocin

  摘要：

  A stereoselective approach to the advanced precursor of (+)-myriocin, 3-deoxy-1,2:5,6-di-O-isopropylidene-3-methoxycarbonylamino-alpha-D-glucofuranose 3-C-carboxylic acid, via the [3,3]-sigmatropic rearrangement of allylic thiocyanates prepared from D-glucose is presented. From the observed results, supported by DFT calculations, we can conclude that the [3,3]-sigmatropic rearrangement of the thiocyanato group in allylic hexofuranosides is strongly influenced by the steric interaction of the 1,2-O-isopropylidene group in the transition states. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.06.032
• 作为产物：
  描述：

  3-deoxy-3-C-[(Z)-(methoxycarbonyl)methylene]-1,2:5,6-di-O-isopropylidene-α-D-glucofuranose 在 咪唑 、 4-二甲氨基吡啶 、 Amberlite IR 120H 、 水 、 二异丁基氢化铝 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 30.92h， 生成 5,6-bis(O-tert-butyldimethylsilyl)-3-deoxy-1,2-O-isopropylidene-3-C-(Z)-(2-thiocyanatoethylidene)-α-D-glucofuranose
  参考文献：
  名称：

  Creation of quarternary stereocentres via [3,3]-sigmatropic rearrangement of allylic thiocyanates. A synthetic approach to (+)-myriocin

  摘要：

  A stereoselective approach to the advanced precursor of (+)-myriocin, 3-deoxy-1,2:5,6-di-O-isopropylidene-3-methoxycarbonylamino-alpha-D-glucofuranose 3-C-carboxylic acid, via the [3,3]-sigmatropic rearrangement of allylic thiocyanates prepared from D-glucose is presented. From the observed results, supported by DFT calculations, we can conclude that the [3,3]-sigmatropic rearrangement of the thiocyanato group in allylic hexofuranosides is strongly influenced by the steric interaction of the 1,2-O-isopropylidene group in the transition states. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.06.032