(1R,2R,3S,4S,5S)-4-O-acetyl-5-(benzoyloxymethyl)-3-O-(tert-butyldimethylsilyl)-1,2-O-cyclohexylidenecyclohexane-1,2,3,4,5-pentol | 175979-28-9

• 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: (1R,2R,3S,4S,5S)-4-O-acetyl-5-(benzoyloxymethyl)-3-O-(tert-butyldimethylsilyl)-1,2-O-cyclohexylidenecyclohexane-1,2,3,4,5-pentol
• CAS: 175979-28-9
• 化学式: C₂₈H₄₂O₈Si
• 分子量: 534.722
• InChiKey: FUAGVCQVNTVIAH-AHPXAKOISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.74
• 重原子数：
  37.0
• 可旋转键数：
  6.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  100.52
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  (1R,2R,3S,4S,5S)-4-O-acetyl-5-(benzoyloxymethyl)-3-O-(tert-butyldimethylsilyl)-1,2-O-cyclohexylidenecyclohexane-1,2,3,4,5-pentol 在 磺酰氯 、 四丁基氟化铵 、 氧气 、 焦磷酸硫胺素 、 N,N'-硫羰基二咪唑 、 三氟乙酸 、 三甲氧基磷 作用下， 以 四氢呋喃 、 吡啶 、 四氯化碳 、 二氯甲烷 、 水 为溶剂， 反应 63.5h， 生成 [(1R,4R,7S,8S)-7-acetyloxy-8-hydroxy-2,3-dioxabicyclo[2.2.2]oct-5-en-1-yl]methyl benzoate
  参考文献：
  名称：

  Enantiospecific Syntheses of (+)-Crotepoxide, (+)-Boesenoxide, (+)-β-Senepoxide, (+)-Pipoxide Acetate, (−)-iso-Crotepoxide, (−)-Senepoxide, and (−)-Tingtanoxide from (−)-Quinic Acid¹

  摘要：

  A convenient strategy that is ideally suited for the construction of all the naturally occurring cyclohexane diepoxides and cyclohexene epoxides is described. The key intermediate 12, a 1,3-cyclohexadiene, has been prepared from (-)-quinic acid in 11 steps with 18% overall yield. Singlet oxygen photooxygenation of the 1,3-cyclohexadiene followed by rearrangement of the resultant endoperoxides with either cobalt-meso-tetraphenylporphyrin or trimethyl phosphite afforded enantiopure (+)-crotepoxide, (+)-boesenoxide, and (-)-iso-crotepoxide or (-)-senepoxide, (+)-beta-senepoxide,(+)-pipoxide acetate, and (-)-tingtanoxide, respectively.

  DOI：

  10.1021/jo970907o
• 作为产物：
  描述：

  (1R,2R,3S)-1,2-O-Cyclohexylidene-5-hydroxymethyl-4-cyclohexen-1,2,3-triol 在 咪唑 、 2,3,5-三甲基吡啶 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 sodium periodate 作用下， 以 吡啶 、 二氯甲烷 、 乙酸乙酯 、 乙腈 为溶剂， 反应 26.05h， 生成 (1R,2R,3S,4S,5S)-4-O-acetyl-5-(benzoyloxymethyl)-3-O-(tert-butyldimethylsilyl)-1,2-O-cyclohexylidenecyclohexane-1,2,3,4,5-pentol
  参考文献：
  名称：

  Enantiospecific Syntheses of (+)-Crotepoxide, (+)-Boesenoxide, (+)-β-Senepoxide, (+)-Pipoxide Acetate, (−)-iso-Crotepoxide, (−)-Senepoxide, and (−)-Tingtanoxide from (−)-Quinic Acid¹

  摘要：

  A convenient strategy that is ideally suited for the construction of all the naturally occurring cyclohexane diepoxides and cyclohexene epoxides is described. The key intermediate 12, a 1,3-cyclohexadiene, has been prepared from (-)-quinic acid in 11 steps with 18% overall yield. Singlet oxygen photooxygenation of the 1,3-cyclohexadiene followed by rearrangement of the resultant endoperoxides with either cobalt-meso-tetraphenylporphyrin or trimethyl phosphite afforded enantiopure (+)-crotepoxide, (+)-boesenoxide, and (-)-iso-crotepoxide or (-)-senepoxide, (+)-beta-senepoxide,(+)-pipoxide acetate, and (-)-tingtanoxide, respectively.

  DOI：

  10.1021/jo970907o

文献信息

• First enantiospecific syntheses of crotepoxide and iso-crotepoxide from (−)-quinic acid
  作者：Tony K.M Shing、Eric K.W Tam

  DOI：10.1016/0957-4166(96)00004-3

  日期：1996.2

  The optically active crotepoxide 1 and iso-crotepoxide 2 have been constructed from quinic acid involving a singlet oxygen photooxygentation as the key step.