展青霉酯C | 103654-47-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 中文名称: 展青霉酯C
• 英文名称: (Z)-Isopatulolide C
• 英文别名: Patulolide C；(3Z,5S,12R)-5-hydroxy-12-methyl-1-oxacyclododec-3-en-2-one
• CAS: 103654-47-3
• 化学式: C₁₂H₂₀O₃
• 分子量: 212.289
• InChiKey: KANOICQRSIXTJU-XJMUJKMXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  2-(hex-5-yn-1-yloxy)tetrahydro-2H-pyran 在 4-二甲氨基吡啶 、 palladium on activated charcoal 吡啶 、 咪唑 、 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 ruthenium trichloride 、 lithium hydroxide 、 sodium periodate 、 正丁基锂 、 草酰氯 、 4 A molecular sieve 、 四丁基氟化铵 、 氢气 、 四丁基碘化铵 、 sodium hydride 、 二异丁基氢化铝 、 对甲苯磺酸 、 二甲基亚砜 、 (+)-Weinsaeure-diethylester 、 三乙胺 、 N,N-二异丙基乙胺 、 2,6-二氯苯甲酰氯 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 四氯化碳 、 六甲基磷酰三胺 、 乙醚 、 乙醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 141.58h， 生成 展青霉酯C
  参考文献：
  名称：

  Total synthesis of patulolide C and its homo-, nor, and iso analogs

  摘要：

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.

  DOI：

  10.1021/jo00077a047

文献信息

• Total synthesis of patulolide C and its homo-, nor, and iso analogs
  作者：Frank M. C. Leemhuis、Lambertus Thijs、Binne Zwanenburg

  DOI：10.1021/jo00077a047

  日期：1993.12

  The stereospecific total synthesis of the naturally occurring macrolide patulolide C 19Eb as well as its iso, nor, and homo analogs is described by applying the photoinduced rearrangement of enantiomerically pure epoxy diazomethyl ketones 14 to gamma-hydroxy alpha,beta-unsaturated esters 15 as the key step. The required epoxy diazomethyl ketones 14 are obtained by a Sharpless epoxidation of an appropriate allylic alcohol, followed by ruthenium tetraoxide oxidation to an oxiranecarboxylic acid, conversion into a mixed anhydride, and treatment with diazomethane. Macrolide 19Zb, which is a geometrical isomer of 19Eb, turned out to be a diastereomer of natural macrolide isopatulolide C, which implies the 4R,11R configuration for this natural material. X-ray diffraction analyses of 19Ea and 19Eb show that there is a considerable difference in spatial arrangement; particularly, the different torsion angles between the carbonyl and olefinic bonds are note worthy. The conformational behavior of these macrolides is also deduced from the NMR and UV spectra.