Acetic acid (1R,4S,4aS,8aR)-8-acetoxy-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methano-naphthalen-5-yl ester | 199594-25-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: Acetic acid (1R,4S,4aS,8aR)-8-acetoxy-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methano-naphthalen-5-yl ester
• 英文别名: [(1S,2S,7R,8R)-6-acetyloxy-1,8,9,10-tetrachloro-11,11-dimethoxy-3-tricyclo[6.2.1.02,7]undeca-3,5,9-trienyl] acetate
• CAS: 199594-25-7
• 化学式: C₁₇H₁₆Cl₄O₆
• 分子量: 458.122
• InChiKey: NXPXOIKGBDWKAM-HMEQZMJYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  Acetic acid (1R,4S,4aS,8aR)-8-acetoxy-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methano-naphthalen-5-yl ester 在 盐酸 、 cerium(III) chloride 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 丙酮 、 苯 为溶剂， 反应 83.0h， 生成 11,12-benzo-4,6,7,8-tetrachloro-5,5-dimethoxyheptacyclo[7,7,1,0^2,6.0^3,10.0^4,8.0^7,17.0^11,16]trideca-11-ene-1,10-diol
  参考文献：
  名称：

  Synthetic Approach Towards Hexaprismane. A Novel Entry to Homosecohexaprismane Skeleton by Cage Enlargement

  摘要：

  AbstractA series of caged 1,4‐diols, 26, 29a/29b, 31, were synthesized from the Diels‐Alder cycloadduct 21 of 1,2,3,4‐tetrachloro‐5,5‐dimethoxycyclopentadiene and 1,4‐benzoquinone. Reduction of enedione 21 with aqueous TiCl3, followed by base‐catalyzed enolization in the presence of acetic anhydride, gave diene 23b, which reacted with maleic anhydride and 1,4‐benzoquinone to produce the corresponding [4+2] cycloadducts 24b and 27, respectively. The adduct 24b was converted to birdcaged 1,4‐diol 26 by photocyclization followed by decarboxylative olefination of resulted caged anhydride 25b. The adduct 27 was photocyclized to cage compound 28, which was aromatized to dihydroquinone 29a by acid‐catalyzed enolization, or benzo‐annulated compound 31 by reduction and dehydration. The birdcaged 1,4‐diols 26 and 31 underwent fragmentation induced by (diacetoxyiodo)benzene to give enediones 38/39 and 41/42, respectively. Photocyclization of 38 and 39 produced the corresponding caged compounds 43 and 44, respectively, possessing homosecohexaprismane skeletons. The corresponding monohydrate 43a of 43 was structurally characterized by single‐crystal X‐ray diffraction.

  DOI：

  10.1002/jccs.199700073
• 作为产物：
  描述：

  1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione 在 4-二甲氨基吡啶 、 titanium(III) chloride 、 三乙胺 作用下， 以 丙酮 为溶剂， 反应 8.0h， 生成 Acetic acid (1R,4S,4aS,8aR)-8-acetoxy-1,2,3,4-tetrachloro-9,9-dimethoxy-1,4,4a,8a-tetrahydro-1,4-methano-naphthalen-5-yl ester
  参考文献：
  名称：

  Synthetic Approach Towards Hexaprismane. A Novel Entry to Homosecohexaprismane Skeleton by Cage Enlargement

  摘要：

  AbstractA series of caged 1,4‐diols, 26, 29a/29b, 31, were synthesized from the Diels‐Alder cycloadduct 21 of 1,2,3,4‐tetrachloro‐5,5‐dimethoxycyclopentadiene and 1,4‐benzoquinone. Reduction of enedione 21 with aqueous TiCl3, followed by base‐catalyzed enolization in the presence of acetic anhydride, gave diene 23b, which reacted with maleic anhydride and 1,4‐benzoquinone to produce the corresponding [4+2] cycloadducts 24b and 27, respectively. The adduct 24b was converted to birdcaged 1,4‐diol 26 by photocyclization followed by decarboxylative olefination of resulted caged anhydride 25b. The adduct 27 was photocyclized to cage compound 28, which was aromatized to dihydroquinone 29a by acid‐catalyzed enolization, or benzo‐annulated compound 31 by reduction and dehydration. The birdcaged 1,4‐diols 26 and 31 underwent fragmentation induced by (diacetoxyiodo)benzene to give enediones 38/39 and 41/42, respectively. Photocyclization of 38 and 39 produced the corresponding caged compounds 43 and 44, respectively, possessing homosecohexaprismane skeletons. The corresponding monohydrate 43a of 43 was structurally characterized by single‐crystal X‐ray diffraction.

  DOI：

  10.1002/jccs.199700073

文献信息

• A fragmentation-photocyclization approach towards homosecohexaprismane skeleton
  作者：Teh-Chang Chou、Yu-Lin Yeh、Gerng-Horng Lin

  DOI：10.1016/s0040-4039(96)02030-8

  日期：1996.11

  Birdcaged bicyclo[2.2.2]octene-1,4-diol 15 was prepared from Diels-Alder adduct of 5,5-dimethoxy-1,2,3,4-tetrachlorocyclopentadiene in five steps. This diol underwent DIB-promoted fragmentation to give tetracyclic dienes 16 and 17. Intramolecular [2+2]photocyclization of 16 and 17 furnished hexacyclic cage compounds 18 and 19 having homosecohexaprismane skeleton. Copyright (C) 1996 Elsevier Science Ltd