(1S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-[(S)-1,3-dithian-2-yl(hydroxy)methyl]-2,4,4-trimethylcyclohex-2-en-1-ol | 171012-23-0

• 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: (1S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-[(S)-1,3-dithian-2-yl(hydroxy)methyl]-2,4,4-trimethylcyclohex-2-en-1-ol
• CAS: 171012-23-0
• 化学式: C₂₀H₃₈O₃S₂Si
• 分子量: 418.737
• InChiKey: ONJKDVFLUGMJPK-UXLLHSPISA-N

物化性质

• 沸点：
  499.3±45.0 °C(predicted)
• 密度：
  1.10±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.04
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  100
• 氢给体数：
  2
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-[(S)-1,3-dithian-2-yl(hydroxy)methyl]-2,4,4-trimethylcyclohex-2-en-1-ol 在 吡啶 、 4-二甲氨基吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 苯 为溶剂， 反应 24.0h， 生成 [(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)-<(Acetyloxy)methyl>-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 、 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 为溶剂， 反应 31.75h， 生成 (1S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-[(S)-1,3-dithian-2-yl(hydroxy)methyl]-2,4,4-trimethylcyclohex-2-en-1-ol
  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