specionin acetate | 114972-82-6

• 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: specionin acetate
• 英文别名: [(1S,2S,4S,5S,6R,8S,10S)-2-(acetyloxymethyl)-8,10-diethoxy-3,9-dioxatricyclo[4.4.0.02,4]decan-5-yl] 4-hydroxybenzoate
• CAS: 114972-82-6；115016-26-7；115016-27-8；142694-77-7
• 化学式: C₂₂H₂₈O₉
• 分子量: 436.459
• InChiKey: HQVYAPIQSHVWGK-NCEGCGGISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  113
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为产物：
  描述：

  在 palladium on activated charcoal sodium periodate 、 氢气 、 对甲苯磺酸 作用下， 以 乙醇 为溶剂， 25.0 ℃ 、275.79 kPa 条件下， 反应 8.0h， 生成 specionin acetate
  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

• Total synthesis of (±)-specionin
  作者：John Leonard、Nigel Hussain

  DOI：10.1039/p19940000061

  日期：——

  (±)-Specionin has been synthesized in a short, efficient sequence of reactions from (±)-exo, exo-6,7-bis(benzyloxy)-exo-4-(hydroxymethyl)-cis-bicyclo[3.3.0]oct-2-ene 5. The key feature of the synthesis is a ‘one-pot’ hydrogenolysis–cyclopentanediol cleavage–bis-acetal cyclisation on intermediate 21a, to provide specionin acetate stereoselectively. The 1β-H, 3α-H stereochemical arrangement of specionin

  （±）-Specionin已经在很短的被合成，从（±）反应的有效序列-外，外切-6,7-二（苄氧基） -外-4-（羟甲基） -顺式-二环[3.3.0]辛-2-烯5。合成的关键特征是在中间体21a上进行“一锅法”氢解-环戊二醇裂解-双缩醛环化，以立体选择性地提供乙酸血红素。血红蛋白的1β-H，3α-H立体化学排列显示是热力学上优选的，并且在左手环的功能完整的情况下，乙缩醛的立体化学可通过平衡来控制。醋酸specionin，的非对映体26A，也已经从（±）制备-exo，exo -6,7-双（苄氧基）-内-2-（羟甲基）-顺-双环[3.3.0] oct-2-烯6a，通过一系列类似的反应。
• Total synthesis of specionin - natural product or artifact ?
  作者：Nigel Hussain、John Leonard

  DOI：10.1016/s0040-4039(00)96648-6

  日期：1987.1

  The iridoid insect antifeedant specionin has been synthesised from endo-cis-bicyclo[3.3.0]oct-7-en-2-ol. When the bis acetal ring is cyclised at a late stage the correct stereochemistry is generated selectively.

  从内部顺式-双环[3.3.0] oct-7-en-2-ol合成了鸢尾类昆虫拒食性血红蛋白。当双缩醛环在后期被环化时，选择性地产生正确的立体化学。