4-benzoyloxymethyl-3,8-dioxatricyclo[5.1.0.0^2,4]octane-5,6-diol 5-acetate | 175979-34-7

• 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: 4-benzoyloxymethyl-3,8-dioxatricyclo[5.1.0.0^2,4]octane-5,6-diol 5-acetate
• 英文别名: 3-deacetoxycrotepoxide；[1R-(1alpha,2alpha,4alpha,5beta,6alpha,7alpha)]-4-Benzoyloxymethyl-5,6-dihydroxy-3,8-dioxatricyclo[5.1.0.0^2,4^]octan-5-yl acetate；[(1R,2R,4R,5S,6R,7R)-5-acetyloxy-6-hydroxy-3,8-dioxatricyclo[5.1.0.02,4]octan-4-yl]methyl benzoate
• CAS: 175979-34-7
• 化学式: C₁₆H₁₆O₇
• 分子量: 320.299
• InChiKey: JTWOJIAZXXXTER-VHYSLAALSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  23
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  97.9
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 4-benzoyloxymethyl-3,8-dioxatricyclo[5.1.0.0^2,4]octane-5,6-diol 5-acetate 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以100%的产率得到细叶青蒌藤素
  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)-3-O-tert-Butyldimethylsilyl-1,2-O-cyclohexylidene-5-hydroxymethyl-4-cyclohexen-1,2,3-triol 在 4-二甲氨基吡啶 、 ruthenium trichloride 、 sodium periodate 、 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 、 氯仿 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 78.55h， 生成 4-benzoyloxymethyl-3,8-dioxatricyclo[5.1.0.0^2,4]octane-5,6-diol 5-acetate
  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.
• Enantiospecific Syntheses of (+)-Crotepoxide, (+)-Boesenoxide, (+)-β-Senepoxide, (+)-Pipoxide Acetate, (−)-<i>iso</i>-Crotepoxide, (−)-Senepoxide, and (−)-Tingtanoxide from (−)-Quinic Acid¹
  作者：Tony K. M. Shing、Eric K. W. Tam

  DOI：10.1021/jo970907o

  日期：1998.3.1

  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.