acetic acid (1S,3R,5S,6S)-5-fluoro-6-methyl-7-oxabicyclo[4.1.0]hept-3-yl ester | 214212-11-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧杂环己烷
• 英文名称: acetic acid (1S,3R,5S,6S)-5-fluoro-6-methyl-7-oxabicyclo[4.1.0]hept-3-yl ester
• 英文别名: [(1S,3R,5S,6S)-5-fluoro-6-methyl-7-oxabicyclo[4.1.0]heptan-3-yl] acetate
• CAS: 214212-11-0
• 化学式: C₉H₁₃FO₃
• 分子量: 188.199
• InChiKey: VXFALSJQMNIKSN-XSPKLOCKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  acetic acid (1S,3R,5S,6S)-5-fluoro-6-methyl-7-oxabicyclo[4.1.0]hept-3-yl ester 在 2,2,6,6-四甲基哌啶 、 咪唑 、 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium periodate 、 正丁基锂 、 molecular sieve 、 乙基氯化镁 、 四丁基碘化铵 、 二异丁基氢化铝 、 potassium carbonate 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 甲醇 、 正己烷 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 75.1h， 生成 <3S-(1Z,3β,5α)>-<3-Fluoro-5-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-2-methylenecyclohexylidene>ethanol
  参考文献：
  名称：

  Efficient Fluorination with Tetrabutylammonium Dihydrogen Trifluoride in a Novel Approach toward 1-α-Fluoro-25-hydroxy-vitamin D₃ Analogues

  摘要：

  The known, but hardly accessible, A-ring phosphine oxide 20, a building block for 1-alpha-fluoro-25-hydroxy-vitamin D-3, was prepared by a new route in gram amounts from (S)-(+)-carvone in 20 steps and 0.6% overall yield. Fluorine was introduced at an early stage by the completely regio- and stereoselective trans-diaxial opening of key-epoxide 5 with neat tetrabutylammonium dihydrogen trifluoride at 95 degrees C. The required 2-carbon chain extension of cyclohexanol 13 was accomplished in moderate yield via S-N' substitution with cesium phenylselanyl acetate followed by Ireland-Claisen rearrangement of the resulting ester 15. Spontaneous elimination of the derived phenyl selenoxide led stereorandomly to a 1:1 mixture of dienoates E/Z-17, which was transformed into 20 as previously described.

  DOI：

  10.1021/jo980764l
• 作为产物：
  描述：

  (1S,2S,3R,5R)-2,3-epoxy-5-isopropenyl-2-methylcyclohex-2-enol 在 lithium hydroxide 、 sodium periodate 、 osmium (III) chloride 、 potassium carbonate 、 tetrabutylammonium bifluoride 、 间氯过氧苯甲酸 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 1,2-二氯乙烷 、 甲苯 为溶剂， 反应 220.0h， 生成 acetic acid (1S,3R,5S,6S)-5-fluoro-6-methyl-7-oxabicyclo[4.1.0]hept-3-yl ester
  参考文献：
  名称：

  Efficient Fluorination with Tetrabutylammonium Dihydrogen Trifluoride in a Novel Approach toward 1-α-Fluoro-25-hydroxy-vitamin D₃ Analogues

  摘要：

  The known, but hardly accessible, A-ring phosphine oxide 20, a building block for 1-alpha-fluoro-25-hydroxy-vitamin D-3, was prepared by a new route in gram amounts from (S)-(+)-carvone in 20 steps and 0.6% overall yield. Fluorine was introduced at an early stage by the completely regio- and stereoselective trans-diaxial opening of key-epoxide 5 with neat tetrabutylammonium dihydrogen trifluoride at 95 degrees C. The required 2-carbon chain extension of cyclohexanol 13 was accomplished in moderate yield via S-N' substitution with cesium phenylselanyl acetate followed by Ireland-Claisen rearrangement of the resulting ester 15. Spontaneous elimination of the derived phenyl selenoxide led stereorandomly to a 1:1 mixture of dienoates E/Z-17, which was transformed into 20 as previously described.

  DOI：

  10.1021/jo980764l

文献信息

• Efficient Fluorination with Tetrabutylammonium Dihydrogen Trifluoride in a Novel Approach toward 1-α-Fluoro-25-hydroxy-vitamin D₃ Analogues
  作者：Pierre Barbier、Peter Mohr、Marc Muller、Raffaello Masciadri

  DOI：10.1021/jo980764l

  日期：1998.10.1

  The known, but hardly accessible, A-ring phosphine oxide 20, a building block for 1-alpha-fluoro-25-hydroxy-vitamin D-3, was prepared by a new route in gram amounts from (S)-(+)-carvone in 20 steps and 0.6% overall yield. Fluorine was introduced at an early stage by the completely regio- and stereoselective trans-diaxial opening of key-epoxide 5 with neat tetrabutylammonium dihydrogen trifluoride at 95 degrees C. The required 2-carbon chain extension of cyclohexanol 13 was accomplished in moderate yield via S-N' substitution with cesium phenylselanyl acetate followed by Ireland-Claisen rearrangement of the resulting ester 15. Spontaneous elimination of the derived phenyl selenoxide led stereorandomly to a 1:1 mixture of dienoates E/Z-17, which was transformed into 20 as previously described.