(3S,4S,5S)-5-O-(tert-Butyldimethylsilyl)-3,4-O-cyclohexylidene-1-formyl-5-(3-hexene-1,5-diynyl)-1-cyclohexene-3,4,5-triol | 168784-11-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,4S,5S)-5-O-(tert-Butyldimethylsilyl)-3,4-O-cyclohexylidene-1-formyl-5-(3-hexene-1,5-diynyl)-1-cyclohexene-3,4,5-triol
• 英文别名: (3aS,7S,7aS)-7-[tert-butyl(dimethyl)silyl]oxy-7-[(Z)-hex-3-en-1,5-diynyl]spiro[6,7a-dihydro-3aH-1,3-benzodioxole-2,1'-cyclohexane]-5-carbaldehyde
• CAS: 168784-11-0
• 化学式: C₂₅H₃₄O₄Si
• 分子量: 426.628
• InChiKey: DTKQWYMDOQQYFC-OWMIFAJBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.91
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3S,4S,5S)-5-O-(tert-Butyldimethylsilyl)-3,4-O-cyclohexylidene-1-formyl-5-(3-hexene-1,5-diynyl)-1-cyclohexene-3,4,5-triol 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 以60%的产率得到(-)-(1S,8S,11S,12S)-1-O-(tert-Butyldimethylsilyl)-11,12-O-cyclohexylidenebicyclo<7.3.1>trideca-4,9-diene-2,6-diyn-8-ol
  参考文献：
  名称：

  Construction of the Bicyclic Core Structure of the Enediyne Antibiotic Esperamicin-A1 in Either Enantiomeric Form from (-)-Quinic Acid

  摘要：

  Employed as a common chiral starting material, (-)-quinic acid (7) was converted in a concise manner to both enantiomers of the beta,gamma-unsaturated ketone 12. On the one hand, (+)-12 was obtained by stereospecific borohydride reduction of the conjugated ketone intermediate 9, transketalization, and oxidation of the derived homoallylic alcohol using the Dess-Martin periodinane reagent. Alternatively, dehydration of the tertiary alcohol 13 and oxidation of the free hydroxyl group in 14 furnished (-)-12 in good overall yield. Reaction of (+)-12 with dichlorocerium TMS acetylide was followed by Pd(0)-assisted construction of the acyclic enediyne 21. Cyclization of this intermediate on treatment with KHMDS proved efficient, providing the esperamicin intermediate (-)-22 in 60% isolated yield. In an identical fashion -)-12 was converted to the enantiomeric bicyclic enediyne (+)-22. Subsequent liberation of the diol system, and selective oxidation of the allylic alcohol in 25 gave ketone 26. Reaction of this intermediate with Ph(2)S=NH monohydrate gave aziridine 27 which was readily converted to its carbamate derivative 28 in preparation for aziridine ring opening.

  DOI：

  10.1021/jo00114a025
• 作为产物：
  描述：

  (-)-(3S,4S,5S)-5-O-(tert-Butyldimethylsilyl)-3,4-O-cyclohexylidene-1-formyl-5-<6-(trimethylsilyl)-3-hexene-1,5-diynyl>-1-cyclohexene-3,4,5-triol 在 cesium fluoride 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以88%的产率得到(3S,4S,5S)-5-O-(tert-Butyldimethylsilyl)-3,4-O-cyclohexylidene-1-formyl-5-(3-hexene-1,5-diynyl)-1-cyclohexene-3,4,5-triol
  参考文献：
  名称：

  Construction of the Bicyclic Core Structure of the Enediyne Antibiotic Esperamicin-A1 in Either Enantiomeric Form from (-)-Quinic Acid

  摘要：

  Employed as a common chiral starting material, (-)-quinic acid (7) was converted in a concise manner to both enantiomers of the beta,gamma-unsaturated ketone 12. On the one hand, (+)-12 was obtained by stereospecific borohydride reduction of the conjugated ketone intermediate 9, transketalization, and oxidation of the derived homoallylic alcohol using the Dess-Martin periodinane reagent. Alternatively, dehydration of the tertiary alcohol 13 and oxidation of the free hydroxyl group in 14 furnished (-)-12 in good overall yield. Reaction of (+)-12 with dichlorocerium TMS acetylide was followed by Pd(0)-assisted construction of the acyclic enediyne 21. Cyclization of this intermediate on treatment with KHMDS proved efficient, providing the esperamicin intermediate (-)-22 in 60% isolated yield. In an identical fashion -)-12 was converted to the enantiomeric bicyclic enediyne (+)-22. Subsequent liberation of the diol system, and selective oxidation of the allylic alcohol in 25 gave ketone 26. Reaction of this intermediate with Ph(2)S=NH monohydrate gave aziridine 27 which was readily converted to its carbamate derivative 28 in preparation for aziridine ring opening.

  DOI：

  10.1021/jo00114a025