7-<1-Hydroxy-2,2,4-trimethyl-3-<2-<<2-(trimethylsilyl)ethoxy>methoxy>ethyl>cyclohex-3-enyl>-5-methylhepta-cis-4-trans-6-dienal | 171012-29-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 7-<1-Hydroxy-2,2,4-trimethyl-3-<2-<<2-(trimethylsilyl)ethoxy>methoxy>ethyl>cyclohex-3-enyl>-5-methylhepta-cis-4-trans-6-dienal
• 英文别名: (4Z,6E)-7-[1-hydroxy-2,2,4-trimethyl-3-[2-(2-trimethylsilylethoxymethoxy)ethyl]cyclohex-3-en-1-yl]-5-methylhepta-4,6-dienal
• CAS: 171012-29-6
• 化学式: C₂₅H₄₄O₄Si
• 分子量: 436.707
• InChiKey: WMSCXBJJMMYXBL-GDGWEHBPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.05
• 重原子数：
  30
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  55.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  7-<1-Hydroxy-2,2,4-trimethyl-3-<2-<<2-(trimethylsilyl)ethoxy>methoxy>ethyl>cyclohex-3-enyl>-5-methylhepta-cis-4-trans-6-dienal 在 sodium hypochlorite 、 盐酸羟胺 、 sodium carbonate 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 38.0h， 生成 2,2,4-Trimethyl-1-(4-methyl-3,3a,6,7-tetrahydrobenzoisoxazol-3-yl)-3-<2-<<2-(trimethylsilyl)ethoxy>methoxy>ethyl>cyclohex-3-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
• 作为产物：
  描述：

  (Z)-1-bromo-3-methylpent-2-en-4-yne 在 咪唑 、 lithium aluminium tetrahydride 、 正丁基锂 、 (COCl₂)2 、 二甲基亚砜 、 三乙胺 、 lithium bromide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.83h， 生成 7-<1-Hydroxy-2,2,4-trimethyl-3-<2-<<2-(trimethylsilyl)ethoxy>methoxy>ethyl>cyclohex-3-enyl>-5-methylhepta-cis-4-trans-6-dienal
  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.