(4R,5S,6R)-8-(tert-butyldimethylsilyl)oxy-4-hydroxy-5-methyloct-1-en-6-yl benzoate | 221627-54-9

• 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: (4R,5S,6R)-8-(tert-butyldimethylsilyl)oxy-4-hydroxy-5-methyloct-1-en-6-yl benzoate
• 英文别名: [(3R,4S,5R)-1-[tert-butyl(dimethyl)silyl]oxy-5-hydroxy-4-methyloct-7-en-3-yl] benzoate
• CAS: 221627-54-9
• 化学式: C₂₂H₃₆O₄Si
• 分子量: 392.611
• InChiKey: BDINUAFZSSJAEU-DFQSSKMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  27.0
• 可旋转键数：
  10.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  55.76
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (4R,5S,6R)-8-(tert-butyldimethylsilyl)oxy-4-hydroxy-5-methyloct-1-en-6-yl benzoate 在 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 氢氟酸 、 二异丁基氢化铝 作用下， 以 吡啶 、 乙醚 、 二氯甲烷 为溶剂， 生成 [(3R,4R,5R)-3-hydroxy-4-methyl-5-tri(propan-2-yl)silyloxyoct-7-enyl] 2,2-dimethylpropanoate
  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：

  3-(叔丁基-二甲基-硅烷基OXY)-丙醛 在 吡啶 、 (+)-Ipc₂BOMe 、 正丁基锂 、 potassium tert-butylate 、 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.77h， 生成 (4R,5S,6R)-8-(tert-butyldimethylsilyl)oxy-4-hydroxy-5-methyloct-1-en-6-yl benzoate
  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