N-fluoropyridinium-3-sulfonate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: N-fluoropyridinium-3-sulfonate
• 英文别名: 1-Fluoropyridin-1-ium-3-sulfonate
• 化学式: C₅H₄FNO₃S
• 分子量: 177.156
• InChiKey: WDHBFKGGPXPMGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  69.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  3-吡啶磺酸 在 Amberlite IRA-94S 、 fluorine 作用下， 以 various solvent(s) 为溶剂， 以87%的产率得到N-fluoropyridinium-3-sulfonate
  参考文献：
  名称：

  Highly Selective Fluorinating Agents: a Counteranion-Bound N-Fluoropyridinium Salt System

  摘要：

  A series of alkyl- or (trifluoromethyl)-substituted N-fluoropyridinium-2-sulfonates 2a-h, differing in fluorinating power, were synthesized, and assessment was made of the effectiveness of each selective fluorinating agent. N-Fluoropyridinium-3- and -4-sulfonates 3 and 4 were also synthesized. Power-variables 2a-h were found to be highly selective fluorinating agents for a wide range of nucleophilic substrates such as activated aromatics, enol trialkylsilyl and alkyl ethers, active methylene compounds, activated olefins, and sulfides. Thus, phenol, naphthol, phenylurethane, and the trimethylsilyl ether of phenol were exclusively or highly selectively fluorinated at the o-position with 2f-h. Conjugated enol trialkylsilyl ethers of a steroid were regioselectively fluorinated at the 6-position with moderately powerful 2b-e. This regioselectivity increased with the bulkiness of the silyl part, and with the most bulky triisopropylsilyl group exclusive B-fluorination was achieved. Preferential beta-stereoselective fluorination at the 6-position was observed. N-Fluoropyridinium-2-sulfonates were activated with an acid. This acid-catalyzed fluorination led to the preferential p-fluorination of anisole. The present results can be explained based on the capacity of the 2-sulfonate anion to interact with the hydroxy group of phenol or naphthol, NH group of phenylurethane, silicon atoms of silyl ethers, or protons of acids.

  DOI：

  10.1021/jo00125a049

文献信息

• Highly Selective Fluorinating Agents: a Counteranion-Bound N-Fluoropyridinium Salt System
  作者：Teruo Umemoto、Ginjiro Tomizawa

  DOI：10.1021/jo00125a049

  日期：1995.10

  A series of alkyl- or (trifluoromethyl)-substituted N-fluoropyridinium-2-sulfonates 2a-h, differing in fluorinating power, were synthesized, and assessment was made of the effectiveness of each selective fluorinating agent. N-Fluoropyridinium-3- and -4-sulfonates 3 and 4 were also synthesized. Power-variables 2a-h were found to be highly selective fluorinating agents for a wide range of nucleophilic substrates such as activated aromatics, enol trialkylsilyl and alkyl ethers, active methylene compounds, activated olefins, and sulfides. Thus, phenol, naphthol, phenylurethane, and the trimethylsilyl ether of phenol were exclusively or highly selectively fluorinated at the o-position with 2f-h. Conjugated enol trialkylsilyl ethers of a steroid were regioselectively fluorinated at the 6-position with moderately powerful 2b-e. This regioselectivity increased with the bulkiness of the silyl part, and with the most bulky triisopropylsilyl group exclusive B-fluorination was achieved. Preferential beta-stereoselective fluorination at the 6-position was observed. N-Fluoropyridinium-2-sulfonates were activated with an acid. This acid-catalyzed fluorination led to the preferential p-fluorination of anisole. The present results can be explained based on the capacity of the 2-sulfonate anion to interact with the hydroxy group of phenol or naphthol, NH group of phenylurethane, silicon atoms of silyl ethers, or protons of acids.