(Z)-(4S,6R,7R,8S,9S,16S)-8-(tert-Butyl-dimethyl-silanyloxy)-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4-triethylsilanyloxy-6-triphenylsilanyloxy-oxacyclohexadec-13-en-2-one | 188259-84-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (Z)-(4S,6R,7R,8S,9S,16S)-8-(tert-Butyl-dimethyl-silanyloxy)-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4-triethylsilanyloxy-6-triphenylsilanyloxy-oxacyclohexadec-13-en-2-one
• CAS: 188259-84-9
• 化学式: C₅₆H₈₃NO₅SSi₃
• 分子量: 966.601
• InChiKey: CTYRGSFRXRQGIJ-DBFIZHRQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  13.42
• 重原子数：
  66.0
• 可旋转键数：
  14.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  66.88
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  (Z)-(4S,6R,7R,8S,9S,16S)-8-(tert-Butyl-dimethyl-silanyloxy)-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4-triethylsilanyloxy-6-triphenylsilanyloxy-oxacyclohexadec-13-en-2-one 在 2,6-二甲基吡啶 、 氟化氢吡啶 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 (4S,6R,7S,8S,9S,16S,Z)-4,8-bis((tert-butyldimethylsilyl)oxy)-6-hydroxy-5,5,7,9-tetramethyl-16-((E)-1-(2-methylthiazol-4-yl)prop-1-en-2-yl)oxacyclohexadec-13-en-2-one
  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,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 作用下， 以 苯 为溶剂， 反应 4.0h， 生成 (Z)-(4S,6R,7R,8S,9S,16S)-8-(tert-Butyl-dimethyl-silanyloxy)-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4-triethylsilanyloxy-6-triphenylsilanyloxy-oxacyclohexadec-13-en-2-one 、 (E)-(4S,6R,7R,8S,9S,16S)-8-(tert-Butyl-dimethyl-silanyloxy)-5,5,7,9-tetramethyl-16-[(E)-1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl]-4-triethylsilanyloxy-6-triphenylsilanyloxy-oxacyclohexadec-13-en-2-one
  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