| 1613336-45-0

• CAS: 1613336-45-0
• 化学式: C₁₂H₁₀NO₄S₂*C₃₇H₄₀FFeN₂O
• 分子量: 899.931
• InChiKey: FXSINICORJCGBA-YGEMNEKTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  cesium carba-closo-dodecaborate 、 以 二氯甲烷 、 乙腈 为溶剂， 反应 0.5h， 生成
  参考文献：
  名称：

  Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the α-Fluorination of Ketenes: Synthetic and Mechanistic Studies

  摘要：

  The catalytic asymmetric synthesis of alkyl fluorides, particularly alpha-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C6F5ONa to furnish tertiary alpha-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C6F5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an alpha-fluoro-N-acylpyridinium salt, have been examined.

  DOI：

  10.1021/ja5044209
• 作为产物：
  描述：

  N-氟代双苯磺酰胺 、 (S)-(-)-4-吡咯烷吡啶基L(五甲基环戊二烯)铁 、 phenyl benzyl ketene 以 四氢呋喃 为溶剂， 反应 0.5h， 以190 mg的产率得到
  参考文献：
  名称：

  Enantioselective Nucleophile-Catalyzed Synthesis of Tertiary Alkyl Fluorides via the α-Fluorination of Ketenes: Synthetic and Mechanistic Studies

  摘要：

  The catalytic asymmetric synthesis of alkyl fluorides, particularly alpha-fluorocarbonyl compounds, has been the focus of substantial effort in recent years. While significant progress has been described in the formation of enantioenriched secondary alkyl fluorides, advances in the generation of tertiary alkyl fluorides have been more limited. Here, we describe a method for the catalytic asymmetric coupling of aryl alkyl ketenes with commercially available N-fluorodibenzenesulfonimide (NFSI) and C6F5ONa to furnish tertiary alpha-fluoroesters. Mechanistic studies are consistent with the hypothesis that the addition of an external nucleophile (C6F5ONa) is critical for turnover, releasing the catalyst (PPY*) from an N-acylated intermediate. The available data can be explained by a reaction pathway wherein the enantioselectivity is determined in the turnover-limiting transfer of fluorine from NFSI to a chiral enolate derived from the addition of PPY* to the ketene. The structure and the reactivity of the product of this proposed elementary step, an alpha-fluoro-N-acylpyridinium salt, have been examined.

  DOI：

  10.1021/ja5044209