(2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-3,5-<(p-bromobenzylidene)dioxy>-9,11-dihydroxy-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide | 160796-76-9

• 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
• 英文名称: (2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-3,5-<(p-bromobenzylidene)dioxy>-9,11-dihydroxy-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide
• CAS: 160796-76-9
• 化学式: C₂₇H₃₉BrO₆
• 分子量: 539.507
• InChiKey: GTZCLILZTCTRPF-RACDZNPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.03
• 重原子数：
  34.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  85.22
• 氢给体数：
  2.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-3,5-<(p-bromobenzylidene)dioxy>-9,11-dihydroxy-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide 在 二甲基二环氧乙烷 作用下， 以 丙酮 为溶剂， 以100%的产率得到(2R,3S,4R,5S,6S,8R,9R,10R,11R,12R,13R)-3,5-<(p-bromobenzylidene)dioxy>-8,8-(epoxymethano)-9,11-dihydroxy-2,4,6,10,12,13-hexamethyltetradecanolide
  参考文献：
  名称：

  Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one

  摘要：

  A highly stereocontrolled total synthesis of oleandolide (2), the aglycon of the macrolide antibiotic oleandomycin (1), has been completed in 8% overall yield (20 steps longest Linear sequence, 26 steps in total) with 90% overall diastereoselectivity. Initially, reagent-controlled syn aldol reactions of (S)-1-(benzyloxy)-2-methylpentan-3-one ((S)-8) were employed to prepare adducts 6 (SS) and 7 (SA), which were elaborated to provide the two advanced fragments 33 and 27, respectively. Coupling of these fragments followed by functional group manipulation and macrolactonization gave the macrocyclic ketone 42, possessing S configuration at C-9. Elaboration of 42 to oleandolide, however, proved troublesome. Substrate-controlled syn and anti aldol reactions of ketone (S)-8, meanwhile, provided the adducts 6 (SS) and 7 (AA), which enabled synthesis, via fragments 64 and 60, of the key macrocyclic ketone intermediate 69, having R configuration at C-9. Stereoselective epoxidation of ketone 69, by reaction with dimethylsulfonium methylide under macrocyclic stereocontrol, provided the (8R)-epoxide 83; subsequent elaboration then gave oleandolide (2).

  DOI：

  10.1021/ja00104a010
• 作为产物：
  描述：

  4-溴苯甲醛二甲缩醛 、 (2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-3,5,9,11-tetrahydroxy-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide 在 camphor-10-sulfonic acid 作用下， 以 二氯甲烷 为溶剂， 反应 0.75h， 以89%的产率得到(2R,3S,4R,5S,6S,9R,10R,11R,12R,13R)-3,5-<(p-bromobenzylidene)dioxy>-9,11-dihydroxy-2,4,6,10,12,13-hexamethyl-8-methylenetetradecanolide
  参考文献：
  名称：

  Studies in Macrolide Synthesis: A Stereocontrolled Synthesis of Oleandolide Employing Reagent- and Substrate-Controlled Aldol Reactions of (S)-1-(Benzyloxy)-2-methylpentan-3-one

  摘要：

  A highly stereocontrolled total synthesis of oleandolide (2), the aglycon of the macrolide antibiotic oleandomycin (1), has been completed in 8% overall yield (20 steps longest Linear sequence, 26 steps in total) with 90% overall diastereoselectivity. Initially, reagent-controlled syn aldol reactions of (S)-1-(benzyloxy)-2-methylpentan-3-one ((S)-8) were employed to prepare adducts 6 (SS) and 7 (SA), which were elaborated to provide the two advanced fragments 33 and 27, respectively. Coupling of these fragments followed by functional group manipulation and macrolactonization gave the macrocyclic ketone 42, possessing S configuration at C-9. Elaboration of 42 to oleandolide, however, proved troublesome. Substrate-controlled syn and anti aldol reactions of ketone (S)-8, meanwhile, provided the adducts 6 (SS) and 7 (AA), which enabled synthesis, via fragments 64 and 60, of the key macrocyclic ketone intermediate 69, having R configuration at C-9. Stereoselective epoxidation of ketone 69, by reaction with dimethylsulfonium methylide under macrocyclic stereocontrol, provided the (8R)-epoxide 83; subsequent elaboration then gave oleandolide (2).

  DOI：

  10.1021/ja00104a010