[(1E,3S)-2-methyl-1-(2-methyl-1,3-thiazol-4-yl)hexa-1,5-dien-3-yl] (3S,5R,6R,7S,8S)-7-[tert-butyl(dimethyl)silyl]oxy-4,4,6,8-tetramethyl-3-triethylsilyloxy-5-triphenylsilyloxytridec-12-enoate | 188259-73-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: [(1E,3S)-2-methyl-1-(2-methyl-1,3-thiazol-4-yl)hexa-1,5-dien-3-yl] (3S,5R,6R,7S,8S)-7-[tert-butyl(dimethyl)silyl]oxy-4,4,6,8-tetramethyl-3-triethylsilyloxy-5-triphenylsilyloxytridec-12-enoate
• CAS: 188259-73-6
• 化学式: C₅₈H₈₇NO₅SSi₃
• 分子量: 994.655
• InChiKey: USDVYZMUPXZHGQ-BHNJLHNJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  14.22
• 重原子数：
  68
• 可旋转键数：
  30
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  95.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  [(1E,3S)-2-methyl-1-(2-methyl-1,3-thiazol-4-yl)hexa-1,5-dien-3-yl] (3S,5R,6R,7S,8S)-7-[tert-butyl(dimethyl)silyl]oxy-4,4,6,8-tetramethyl-3-triethylsilyloxy-5-triphenylsilyloxytridec-12-enoate 在 RuBnCl₂(PCy₃)2 2,6-二甲基吡啶 、 戴斯-马丁氧化剂 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 8.0h， 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：

  (S,E)-2-methyl-1-(2-methylthiazol-4-yl)hexa-1,5-dien-3-ol 在 咪唑 、 4-二甲氨基吡啶 、 sodium tetrahydroborate 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 生成 [(1E,3S)-2-methyl-1-(2-methyl-1,3-thiazol-4-yl)hexa-1,5-dien-3-yl] (3S,5R,6R,7S,8S)-7-[tert-butyl(dimethyl)silyl]oxy-4,4,6,8-tetramethyl-3-triethylsilyloxy-5-triphenylsilyloxytridec-12-enoate
  参考文献：
  名称：

  Remote Effects in Macrolide Formation through Ring-Forming Olefin Metathesis:  An Application to the Synthesis of Fully Active Epothilone Congeners

  摘要：

  DOI：

  10.1021/ja964275j

文献信息

• Total Syntheses of Epothilones A and B
  作者：Dongfang Meng、Peter Bertinato、Aaron Balog、Dai-Shi Su、Ted Kamenecka、Erik J. Sorensen、Samuel J. Danishefsky

  DOI：10.1021/ja971946k

  日期：1997.10.1

  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.
• Remote Effects in Macrolide Formation through Ring-Forming Olefin Metathesis:  An Application to the Synthesis of Fully Active Epothilone Congeners
  作者：Dongfang Meng、Dai-Shi Su、Aaron Balog、Peter Bertinato、Erik J. Sorensen、Samuel J. Danishefsky、Yu-Huang Zheng、Ting-Chao Chou、Lifeng He、Susan B. Horwitz

  DOI：10.1021/ja964275j

  日期：1997.3.1