[(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-hydroxy-4,4,7-trimethyloct-1-en-3-yl] acetate | 861120-02-7

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-hydroxy-4,4,7-trimethyloct-1-en-3-yl] acetate
• CAS: 861120-02-7
• 化学式: C₂₉H₄₂O₄Si
• 分子量: 482.736
• InChiKey: MCTVPOUQPAAOAO-GDKKVTFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  34
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-hydroxy-4,4,7-trimethyloct-1-en-3-yl] acetate 在 2,6-二甲基吡啶 、 四丁基氟化铵 、 戴斯-马丁氧化剂 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 为溶剂， 反应 27.5h， 生成 (2R,4R)-2,5,5-trimethyl-6-oxo-4-(triisopropylsilyl)oxyoct-7-enyl acetate
  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
• 作为产物：
  描述：

  (S)-(+)-泛解酸内酯 在 lithium aluminium tetrahydride 、 正丁基锂 、 samarium diiodide 、 草酰氯 、 4-甲基苯磺酸吡啶 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 27.84h， 生成 [(3R,5R,7R)-8-[tert-butyl(diphenyl)silyl]oxy-5-hydroxy-4,4,7-trimethyloct-1-en-3-yl] acetate
  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