5(R)-<<(1',1'-Dimethylethyl)dimethylsilyl>oxy>-3(S)-hydroxy-2,6,6-trimethylcyclohexen-1-carboxaldehyde | 171012-26-3

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 5(R)-<<(1',1'-Dimethylethyl)dimethylsilyl>oxy>-3(S)-hydroxy-2,6,6-trimethylcyclohexen-1-carboxaldehyde
• 英文别名: (3S,5R)-5-[tert-butyl(dimethyl)silyl]oxy-3-hydroxy-2,6,6-trimethylcyclohexene-1-carbaldehyde
• CAS: 171012-26-3
• 化学式: C₁₆H₃₀O₃Si
• 分子量: 298.498
• InChiKey: DHRNYNVUYUHMEL-UONOGXRCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.68
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5(R)-<<(1',1'-Dimethylethyl)dimethylsilyl>oxy>-3(S)-hydroxy-2,6,6-trimethylcyclohexen-1-carboxaldehyde 在 正丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 反应 3.5h， 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
• 作为产物：
  描述：

  3(S)-(Hydroxymethyl)-2,2,4-trimethylcyclohex-3-en-1(R)-ol 在 4-二甲氨基吡啶 、 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 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 30.25h， 生成 5(R)-<<(1',1'-Dimethylethyl)dimethylsilyl>oxy>-3(S)-hydroxy-2,6,6-trimethylcyclohexen-1-carboxaldehyde
  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

文献信息

• 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
  作者：L. Alcaraz、J. J. Harnett、C. Mioskowski、T. Le Gall、Dong-Soo Shin、J. R. Falck

  DOI：10.1021/jo00127a028

  日期：1995.11

  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.