(2R)-trans-2-acetoxy-3-hydroxy-1-[(benzoyloxy)methyl]cyclohexa-4,6-diene | 96247-02-8

• 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: (2R)-trans-2-acetoxy-3-hydroxy-1-[(benzoyloxy)methyl]cyclohexa-4,6-diene
• 英文别名: [(5R,6R)-6-acetyloxy-5-hydroxycyclohexa-1,3-dien-1-yl]methyl benzoate
• CAS: 96247-02-8
• 化学式: C₁₆H₁₆O₅
• 分子量: 288.3
• InChiKey: JUCWKHGPKAOLHQ-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  72.8
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R)-trans-2-acetoxy-3-hydroxy-1-[(benzoyloxy)methyl]cyclohexa-4,6-diene 在 4-二甲氨基吡啶 、 氧气 、 焦磷酸硫胺素 、 三乙胺 作用下， 以 四氯化碳 、 二氯甲烷 、 氯仿 为溶剂， 反应 19.0h， 生成 α-senepoxide
  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 、 氢氟酸 、 N,N'-硫羰基二咪唑 、 三氟乙酸 、 三甲氧基磷 作用下， 以 吡啶 、 二氯甲烷 、 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 74.55h， 生成 (2R)-trans-2-acetoxy-3-hydroxy-1-[(benzoyloxy)methyl]cyclohexa-4,6-diene
  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

• Total Synthesis of (±)-Zeylena
  作者：Seiichiro Ogawa、Tohei Takagaki

  DOI：10.1246/bcsj.59.655

  日期：1986.2

  Zeylena, isolated from the roots of Uvaria zeylanica L. (Annonaceae), has been synthesized as a racemic modification by an intramolecular cyclo-addition reaction of DL-trans-2,3-dihydroxy-1-(benzoyloxymethyl)cyclohexa-4,6-diene 3-(E)-cinnamate or its acetate.

  Zeylena，从 Uvaria zeylanica L.（番荔枝科）的根中分离出来，已通过 DL-trans-2,3-dihydroxy-1-(benzoyloxymethyl)cyclohexa-4,6 的分子内环加成反应合成为外消旋修饰-二烯3-(E)-肉桂酸酯或其乙酸酯。
• Total synthesis of (+)-pipoxide and (+)-.beta.-senepoxide and their diene precursors
  作者：Seiichiro Ogawa、Tohei Takagaki

  DOI：10.1021/jo00213a030

  日期：1985.6
• 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.
• Total synthesis and absolute configuration of zeylena
  作者：Seiichiro Ogawa、Tohei Takagaki

  DOI：10.1021/jo00225a015

  日期：1985.12
• 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.