tert-butyl (3S,5R,6S,7S,8S)-7-((tert-butyldimethylsilyl)oxy)-3,5-dihydroxy-4,4,6,8-tetramethylundec-10-enoate | 197233-46-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羟基酸及其衍生物
• 英文名称: tert-butyl (3S,5R,6S,7S,8S)-7-((tert-butyldimethylsilyl)oxy)-3,5-dihydroxy-4,4,6,8-tetramethylundec-10-enoate
• CAS: 197233-46-8
• 化学式: C₂₅H₅₀O₅Si
• 分子量: 458.755
• InChiKey: ZLKXCGKRWMFCHB-HIHICTBBSA-N

物化性质

• 沸点：
  497.0±45.0 °C(Predicted)
• 密度：
  0.957±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  31.0
• 可旋转键数：
  11.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  75.99
• 氢给体数：
  2.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  tert-butyl (3S,5R,6S,7S,8S)-7-((tert-butyldimethylsilyl)oxy)-3,5-dihydroxy-4,4,6,8-tetramethylundec-10-enoate 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 potassium carbonate 、 戴斯-马丁氧化剂 、 氟化氢吡啶 、 三乙胺 、 9-硼双环[3.3.1]壬烷 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 24.75h， 生成 埃博霉素C
  参考文献：
  名称：

  Total Syntheses of Epothilones A and B

  摘要：

  Convergent, stereocontrolled total syntheses of the microtubule-stabilizing macrolides epothilones A (2) and B (3) have been achieved. Four distinct ring-forming strategies were pursued (see Scheme 1). Of these four, three were reduced to practice. In one approach, the action of a base on a substance possessing an acetate ester and a nonenolizable aldehyde brought about a remarkably effective macroaldolization see (89 --> 90 + 91; 99 --> 100 + 101), simultaneously creating the C2-C3 bond and the hydroxyl-bearing stereocenter at C-3. Alternatively, the 16-membered macrolide of the epothilones could be fashioned through a C12-C13 ring-closing olefin metathesis (e.g. see 111 --> 90 + 117; 122 --> 105 + 123) and through macrolactonization of the appropriate hydroxy acid (e.g. see 88 --> 93). The application of a stereospecific B-alkyl Suzuki coupling strategy permitted the establishment of a cis C12-C13 olefin, thus setting the stage for an eventual site-and diastereoselective epoxidation reaction (see 96 --> 2; 106 --> 3). The development of a novel cyclopropane solvolysis strategy for incorporating the geminal methyl groups of the epothilones (see 39 --> 40 --> 41), and the use of Lewis acid catalyzed diene-aldehyde cyclocondensation (LACDAC) (see 35 + 36 --> 37) and asymmetric allylation (see 10 --> 76) methodology are also noteworthy.

  DOI：

  10.1021/ja971946k
• 作为产物：
  描述：

  (1E,3Z)-1-甲氧基-2-甲基-3-(三甲基硅氧基)-1,3-戊二烯 在 吡啶 、 咪唑 、 2,6-二甲基吡啶 、 N-碘代丁二酰亚胺 、 lithium aluminium tetrahydride 、 草酰氯 、 偶氮二异丁腈 、 camphor-10-sulfonic acid 、 diethylzinc 、 三正丁基氢锡 、 四氯化钛 、 对甲苯磺酸 、 氟化氢吡啶 、 二甲基亚砜 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 [双(三氟乙酰氧基)碘]苯 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 9.58h， 生成 tert-butyl (3S,5R,6S,7S,8S)-7-((tert-butyldimethylsilyl)oxy)-3,5-dihydroxy-4,4,6,8-tetramethylundec-10-enoate
  参考文献：
  名称：

  Total Syntheses of Epothilones A and B

  摘要：

  Convergent, stereocontrolled total syntheses of the microtubule-stabilizing macrolides epothilones A (2) and B (3) have been achieved. Four distinct ring-forming strategies were pursued (see Scheme 1). Of these four, three were reduced to practice. In one approach, the action of a base on a substance possessing an acetate ester and a nonenolizable aldehyde brought about a remarkably effective macroaldolization see (89 --> 90 + 91; 99 --> 100 + 101), simultaneously creating the C2-C3 bond and the hydroxyl-bearing stereocenter at C-3. Alternatively, the 16-membered macrolide of the epothilones could be fashioned through a C12-C13 ring-closing olefin metathesis (e.g. see 111 --> 90 + 117; 122 --> 105 + 123) and through macrolactonization of the appropriate hydroxy acid (e.g. see 88 --> 93). The application of a stereospecific B-alkyl Suzuki coupling strategy permitted the establishment of a cis C12-C13 olefin, thus setting the stage for an eventual site-and diastereoselective epoxidation reaction (see 96 --> 2; 106 --> 3). The development of a novel cyclopropane solvolysis strategy for incorporating the geminal methyl groups of the epothilones (see 39 --> 40 --> 41), and the use of Lewis acid catalyzed diene-aldehyde cyclocondensation (LACDAC) (see 35 + 36 --> 37) and asymmetric allylation (see 10 --> 76) methodology are also noteworthy.

  DOI：

  10.1021/ja971946k