(3S,4S,6S)-8-benzyloxy-6-(tert-butyldimethylsilyl)oxy-3-methyloct-1-en-4-ol | 221627-49-2

• 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: (3S,4S,6S)-8-benzyloxy-6-(tert-butyldimethylsilyl)oxy-3-methyloct-1-en-4-ol
• CAS: 221627-49-2
• 化学式: C₂₂H₃₈O₃Si
• 分子量: 378.627
• InChiKey: PNFDDBOWOIHXFJ-JBACZVJFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.56
• 重原子数：
  26.0
• 可旋转键数：
  11.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (3S,4S,6S)-8-benzyloxy-6-(tert-butyldimethylsilyl)oxy-3-methyloct-1-en-4-ol 在 2,6-二甲基吡啶 、 4-甲基苯磺酸吡啶 、 copper dichloride 、 palladium dichloride 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 生成 [(2R,3S,4S,6S)-6-(2-Benzyloxy-ethyl)-3-methyl-4-triisopropylsilanyloxy-tetrahydro-pyran-2-yl]-acetic acid methyl ester
  参考文献：
  名称：

  Intramolecular palladium catalyzed alkoxy carbonylation of 6-hydroxy-1-octenes. Stereoselective synthesis of substituted tetrahydropyrans

  摘要：

  The reaction of hydroxy alkenes 5, 7, and 8 with CO and MeOH in the presence of PdCl2 and CuCl2 gave tetrahydropyrans 9, 11, and 12, respectively. Yields were dependent upon the configuration of substituents in the hydroxy alkene; in all cases, the tetrahydropyran was produced with 2,6-cis configuration. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02693-8
• 作为产物：
  描述：

  异丁基(3S)-5-苄氧基-3-羟基戊酸酯 在 2,6-二甲基吡啶 、 正丁基锂 、 potassium tert-butylate 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 11.5h， 生成 (3S,4S,6S)-8-benzyloxy-6-(tert-butyldimethylsilyl)oxy-3-methyloct-1-en-4-ol
  参考文献：
  名称：

  Total Synthesis of Polycavernoside A, A Lethal Toxin of the Red Alga Polycavernosa tsudai

  摘要：

  Two approaches to the synthesis of the aglycon 120 of polycavernoside A (1) were developed, only one of which was completed. The successful "second-generation" route assembled the aglycon seco acids 102 and 106 via Nozaki-Hiyama-Kishi coupling of aldehyde 70, prepared from methyl (S)3-hydroxy-2-methylpropionate (72) and (S)-pantolactone (73), with vinyl bromide 71. The latter was obtained from a sequence which commenced from the silyl ether 24 of 3-hydroxypropionaldehyde and entailed cyclization of (Z)-zeta -hydroxy-alpha,beta-unsaturated ester 82. Regioselective Yamaguchi lactonization of trihydroxycarboxylic acids 102 and 106 and subsequent functional-group adjustments led to macrolactone 120, to which the fucopyranosylxylopyranoside moiety was attached. Stille coupling of the glycosidated aglycon 128 with dienylstannane 129 furnished polycavernoside A in a synthesis for which the longest linear sequence was 25 steps. The overall yield to lactone 120 was 4.7%.

  DOI：

  10.1021/jo0503862