Acetic acid (1S,5R)-5-(tert-butyl-dimethyl-silanyloxy)-3-((S)-[1,3]dithian-2-yl-hydroxy-methyl)-2,4,4-trimethyl-cyclohex-2-enyl ester | 1025908-50-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: Acetic acid (1S,5R)-5-(tert-butyl-dimethyl-silanyloxy)-3-((S)-[1,3]dithian-2-yl-hydroxy-methyl)-2,4,4-trimethyl-cyclohex-2-enyl ester
• 英文别名: [(1S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-[(S)-1,3-dithian-2-yl(hydroxy)methyl]-2,4,4-trimethylcyclohex-2-en-1-yl] acetate
• CAS: 1025908-50-2
• 化学式: C₂₂H₄₀O₄S₂Si
• 分子量: 460.775
• InChiKey: BNIRANCVHFXTAS-SCTDSRPQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.61
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  106
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-溴苯甲酰氯 、 Acetic acid (1S,5R)-5-(tert-butyl-dimethyl-silanyloxy)-3-((S)-[1,3]dithian-2-yl-hydroxy-methyl)-2,4,4-trimethyl-cyclohex-2-enyl ester 在 吡啶 、 4-二甲氨基吡啶 作用下， 反应 24.0h， 以85%的产率得到[(S)-[(3S,5R)-3-acetyloxy-5-[tert-butyl(dimethyl)silyl]oxy-2,6,6-trimethylcyclohexen-1-yl]-(1,3-dithian-2-yl)methyl] 4-bromobenzoate
  参考文献：
  名称：

  Taxol Total Synthesis: Preparation of a Chiral Ring A Moiety via Biomimetic Cyclization and Evaluation of a Tandem Nitrile Oxide Strategy for Rings B/C

  摘要：

  A fully functionalized taxol ring A moiety 7 was efficiently prepared via biomimetic cation-olefin cyclization of chiral geraniol epoxide 2b using SnCl4 in toluene. Fractional crystallization provided endo-3 (50% yield from 2b) that was converted to aldehyde 5 by stereospecific epoxidation, secondary alcohol protection, and PCC oxidation. NaOMe-mediated ring opening secured enal 6. Addition of lithium dithiane to 6 at low temperature provided 7 as the sole product in good yield. A tandem nitrile oxide cycloaddition strategy for creating the remaining B/C carbocycles as well as key functionality present in both rings was validated, in part, by cyclization of 14 to tricyclic isoxazoline 15.

  DOI：

  10.1021/jo00127a028
• 作为产物：
  描述：

  3(R)-(Hydroxymethyl)-4(R),5(S)-oxido-2,2,4-trimethylcyclohexan-1(R)-ol 在 4-二甲氨基吡啶 、 正丁基锂 、 sodium methylate 、 sodium acetate 、 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 二异丙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 31.75h， 生成 Acetic acid (1S,5R)-5-(tert-butyl-dimethyl-silanyloxy)-3-((S)-[1,3]dithian-2-yl-hydroxy-methyl)-2,4,4-trimethyl-cyclohex-2-enyl ester
  参考文献：
  名称：

  Taxol Total Synthesis: Preparation of a Chiral Ring A Moiety via Biomimetic Cyclization and Evaluation of a Tandem Nitrile Oxide Strategy for Rings B/C

  摘要：

  A fully functionalized taxol ring A moiety 7 was efficiently prepared via biomimetic cation-olefin cyclization of chiral geraniol epoxide 2b using SnCl4 in toluene. Fractional crystallization provided endo-3 (50% yield from 2b) that was converted to aldehyde 5 by stereospecific epoxidation, secondary alcohol protection, and PCC oxidation. NaOMe-mediated ring opening secured enal 6. Addition of lithium dithiane to 6 at low temperature provided 7 as the sole product in good yield. A tandem nitrile oxide cycloaddition strategy for creating the remaining B/C carbocycles as well as key functionality present in both rings was validated, in part, by cyclization of 14 to tricyclic isoxazoline 15.

  DOI：

  10.1021/jo00127a028