ethyl (3aS,3bS,6R,6aR,7aS)-6-hydroxy-2,2-dimethyl-7-oxo-3b,6,6a,7a-tetrahydro-3aH-pentaleno[1,2-d][1,3]dioxole-4-carboxylate | 127085-87-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl (3aS,3bS,6R,6aR,7aS)-6-hydroxy-2,2-dimethyl-7-oxo-3b,6,6a,7a-tetrahydro-3aH-pentaleno[1,2-d][1,3]dioxole-4-carboxylate
• CAS: 127085-87-4；127179-65-1
• 化学式: C₁₄H₁₈O₆
• 分子量: 282.293
• InChiKey: WXQGHTDINOMTKZ-ZROIDTBISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.1
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  82.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl (3aS,3bS,6R,6aR,7aS)-6-hydroxy-2,2-dimethyl-7-oxo-3b,6,6a,7a-tetrahydro-3aH-pentaleno[1,2-d][1,3]dioxole-4-carboxylate 在 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 N,N'-二环己基碳二亚胺 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 7.0h， 生成 (7S,8R)-2-carbethoxy-exo-6-hydroxy-7,8-(isopropylidenedioxy)bicyclo<3.3.0>oct-2-en-exo-4-yl p-(benzyloxy)benzoate
  参考文献：
  名称：

  Chemoenzymic enantiocontrolled synthesis of (-)-specionin

  摘要：

  Specionin acetate la has been synthesized from chlorobenzene in 15 steps and compared with an authentic sample. The chirality was incorporated into the synthesis by microbial dioxygenation of chlorobenzene using a mutant strain of Pseudomonas putida, 39D, to produce 1-chloro-2,3-dihydroxycyclohexa-4,6-diene, which was elaborated into enone 5. Addition of the lithium dienolate derived from ethyl 4-(dimethyl-tert-butylsiloxy)-2-bromocrotonate to this enone provided vinylcyclopropanes 7, which underwent a low-temperature vinylcyclo-propane-cyclopentene rearrangement to tricyclic ketones 8 upon treatment with either trimethylsilyl iodide or tetrabutylammonium fluoride at -78-degrees-C. Following the deoxygenation of the carbonyl and the convergent transformation of both C-4 isomers to a single allylic acetate 11 via either esterification or Mitsunobu inversion, the epoxidation and generation of the bisacetal was accomplished according to the known protocol. The overall yield of this synthesis was 9% for the sequence 5 to 11. Spectral data and experimental details are provided for key compounds.

  DOI：

  10.1021/jo00043a037

文献信息

• Chemoenzymic enantiocontrolled synthesis of (-)-specionin
  作者：Tomas Hudlicky、Michael Natchus

  DOI：10.1021/jo00043a037

  日期：1992.8

  Specionin acetate la has been synthesized from chlorobenzene in 15 steps and compared with an authentic sample. The chirality was incorporated into the synthesis by microbial dioxygenation of chlorobenzene using a mutant strain of Pseudomonas putida, 39D, to produce 1-chloro-2,3-dihydroxycyclohexa-4,6-diene, which was elaborated into enone 5. Addition of the lithium dienolate derived from ethyl 4-(dimethyl-tert-butylsiloxy)-2-bromocrotonate to this enone provided vinylcyclopropanes 7, which underwent a low-temperature vinylcyclo-propane-cyclopentene rearrangement to tricyclic ketones 8 upon treatment with either trimethylsilyl iodide or tetrabutylammonium fluoride at -78-degrees-C. Following the deoxygenation of the carbonyl and the convergent transformation of both C-4 isomers to a single allylic acetate 11 via either esterification or Mitsunobu inversion, the epoxidation and generation of the bisacetal was accomplished according to the known protocol. The overall yield of this synthesis was 9% for the sequence 5 to 11. Spectral data and experimental details are provided for key compounds.