(2R,8S)-2,8-Diisopropenyl-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),10-dien-4-yn-3-one | 180628-32-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: (2R,8S)-2,8-Diisopropenyl-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),10-dien-4-yn-3-one
• 英文别名: (2R,8S)-11-methyl-2,8-bis(prop-1-en-2-yl)-13-oxabicyclo[8.2.1]trideca-1(12),10-dien-4-yn-3-one
• CAS: 180628-32-4
• 化学式: C₁₉H₂₂O₂
• 分子量: 282.382
• InChiKey: WTXARRFJUZKUCA-KXBFYZLASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  30.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,8S)-2,8-Diisopropenyl-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),10-dien-4-yn-3-one 在 二异丁基氢化铝 作用下， 生成 (2S,3R,8S)-2,8-diisopropenyl-11-methyl-13-oxabicyclo[8.2.1]dodeca-3,5-dien-4-yn-3-ol
  参考文献：
  名称：

  Total Synthesis of the Pseudopterane (−)-Kallolide B, the Enantiomer of Natural (+)-Kallolide B

  摘要：

  A total synthesis of the enantiomer 35 of kallolide B was achieved starting from (S)-(-)-perillyl alcohol (8). Oxidative cleavage to the ester aldehyde 11 was effected by treatment of the epoxide 9 with H5IO6 followed by CH2N2. The allenyl ketone 13, obtained by SnCl2-promoted addition of 1-bromo-2-butyne to aldehyde 11 and subsequent Swern oxidation, cyclized to the furan 14 in the presence of catalytic AgNO3. Homologation of the derived aldehyde 15 with CBr4-Ph(3)P followed by n-BuLi and CH2O led to the propargylic alcohol 17, Formylation of the furan 17 (s-BuLi, DMF) and then Still-Horner-Emmons homologation yielded the (Z)-conjugated ester 22. Conversion of the propargylic alcohol function to the chloride 23 and ester reduction (DIBAL-H) furnished the chloro alcohol 24, which formed the cyclic ether 25 upon treatment with NaH. Ether 25 underwent a highly diastereoselective [2,3]Wittig ring contraction to the propargylic alcohol 26. The derived mesylate 36 was converted to the allenic ester 37 with CO and TMSCH(2)CH(2)OH in the presence of Pd(PPh(3))(4). Ester 37 was isomerized to the diastereomer 39 with Ph(3)P in CH3CN. Ester cleavage with TBAF followed by cyclization of the acid intermediate with catalytic AgNO3 led to butenolide 35, identical to kallolide B according to comparison of NMR spectra, but of opposite optical rotation.

  DOI：

  10.1021/jo960798y
• 作为产物：
  描述：

  (S)-(-)-紫苏醇 在 bis(acetylacetonate)oxovanadium 2,6-二甲基吡啶 、 叔丁基过氧化氢 、 正丁基锂 、 草酰氯 、 18-冠醚-6 、 仲丁基锂 、 双(三甲基硅烷基)氨基钾 、 sodium hydride 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 silver nitrate 、 二甲基亚砜 、 甲基磺酰氯 、 高碘酸 、 三苯基膦 、 sodium iodide 、 lithium chloride 、 tin(ll) chloride 作用下， 以 四氢呋喃 、 乙醚 、 癸烷 、 正己烷 、 二氯甲烷 、 环己烷 、 水 、 N,N-二甲基甲酰胺 、 丙酮 、 甲苯 、 正戊烷 为溶剂， 反应 84.1h， 生成 (2R,8S)-2,8-Diisopropenyl-11-methyl-13-oxa-bicyclo[8.2.1]trideca-1(12),10-dien-4-yn-3-one
  参考文献：
  名称：

  Total Synthesis of the Pseudopterane (−)-Kallolide B, the Enantiomer of Natural (+)-Kallolide B

  摘要：

  A total synthesis of the enantiomer 35 of kallolide B was achieved starting from (S)-(-)-perillyl alcohol (8). Oxidative cleavage to the ester aldehyde 11 was effected by treatment of the epoxide 9 with H5IO6 followed by CH2N2. The allenyl ketone 13, obtained by SnCl2-promoted addition of 1-bromo-2-butyne to aldehyde 11 and subsequent Swern oxidation, cyclized to the furan 14 in the presence of catalytic AgNO3. Homologation of the derived aldehyde 15 with CBr4-Ph(3)P followed by n-BuLi and CH2O led to the propargylic alcohol 17, Formylation of the furan 17 (s-BuLi, DMF) and then Still-Horner-Emmons homologation yielded the (Z)-conjugated ester 22. Conversion of the propargylic alcohol function to the chloride 23 and ester reduction (DIBAL-H) furnished the chloro alcohol 24, which formed the cyclic ether 25 upon treatment with NaH. Ether 25 underwent a highly diastereoselective [2,3]Wittig ring contraction to the propargylic alcohol 26. The derived mesylate 36 was converted to the allenic ester 37 with CO and TMSCH(2)CH(2)OH in the presence of Pd(PPh(3))(4). Ester 37 was isomerized to the diastereomer 39 with Ph(3)P in CH3CN. Ester cleavage with TBAF followed by cyclization of the acid intermediate with catalytic AgNO3 led to butenolide 35, identical to kallolide B according to comparison of NMR spectra, but of opposite optical rotation.

  DOI：

  10.1021/jo960798y

文献信息

• Total Synthesis of the Pseudopterane (−)-Kallolide B, the Enantiomer of Natural (+)-Kallolide B
  作者：James A. Marshall、Gary S. Bartley、Eli M. Wallace

  DOI：10.1021/jo960798y

  日期：1996.1.1

  A total synthesis of the enantiomer 35 of kallolide B was achieved starting from (S)-(-)-perillyl alcohol (8). Oxidative cleavage to the ester aldehyde 11 was effected by treatment of the epoxide 9 with H5IO6 followed by CH2N2. The allenyl ketone 13, obtained by SnCl2-promoted addition of 1-bromo-2-butyne to aldehyde 11 and subsequent Swern oxidation, cyclized to the furan 14 in the presence of catalytic AgNO3. Homologation of the derived aldehyde 15 with CBr4-Ph(3)P followed by n-BuLi and CH2O led to the propargylic alcohol 17, Formylation of the furan 17 (s-BuLi, DMF) and then Still-Horner-Emmons homologation yielded the (Z)-conjugated ester 22. Conversion of the propargylic alcohol function to the chloride 23 and ester reduction (DIBAL-H) furnished the chloro alcohol 24, which formed the cyclic ether 25 upon treatment with NaH. Ether 25 underwent a highly diastereoselective [2,3]Wittig ring contraction to the propargylic alcohol 26. The derived mesylate 36 was converted to the allenic ester 37 with CO and TMSCH(2)CH(2)OH in the presence of Pd(PPh(3))(4). Ester 37 was isomerized to the diastereomer 39 with Ph(3)P in CH3CN. Ester cleavage with TBAF followed by cyclization of the acid intermediate with catalytic AgNO3 led to butenolide 35, identical to kallolide B according to comparison of NMR spectra, but of opposite optical rotation.