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2026 26080283

DOI: https://doi.org/10.6023/A26080283

研究论文

金属钴氟络合物催化酰氯/磺酰氯的氟化反应

  • 杨冰彬 ,
  • 巩晨旭 ,
  • 陈烨荣 ,
  • 何星磊 ,
  • 赵彬 ,
  • 余春 ,
  • 叶克印
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  • a福建师范大学 海峡柔性电子（未来科技）学院 福建省柔性电子重点实验室 福州 350117;
    b福州大学 化学学院 有机合成与功能福建省高校重点实验室 福州 350108

收稿日期: 2026-08-12

  网络出版日期: 2026-09-23

基金资助

国家自然科学基金面上项目(22171046).

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Cobalt Fluoride Complex Catalyzed Fluorination of Acyl- and Sulfonyl Chlorides

  • Bing-Bin Yang ,
  • Chen-Xu Gong ,
  • Ye-Rong Chen ,
  • Xing-lei He ,
  • Bin Zhao ,
  • Chun Yu ,
  • Ke-Yin Ye
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  • aFujian Key Laboratory of Flexible Electronics, Strait Institute of Flexible Electronics (SIFE, Future Technologies), Fujian Normal University, Fuzhou, 350117, China;
    bLaboratory of Molecule Synthesis and Function Discovery (Fujian Province University), College of Chemistry, Fuzhou University, Fuzhou 350108

Received date: 2026-08-12

  Online published: 2026-09-23

Supported by

National Natural Science Foundation of China (22171046).

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摘要

酰氟类化合物是重要的有机合成中间体,被广泛应用于药物化学和功能材料等领域。针对现有酰氟合成方法中氟源不稳定、反应条件苛刻及催化剂成本较高等问题,建立了一种以钴氟络合物 [CoF3(terpy)]·MeOH·H2O 为催化剂、 KF 为唯一氟源的氟化体系。该体系可在温和条件下将酰氯及磺酰氯转化为相应的酰氟和磺酰氟,具有操作简便、底物适用范围广及官能团兼容性良好等特点。

关键词： 钴氟络合物; 酰氟; 磺酰氟; 氟化; 氟氯交换

本文引用格式

杨冰彬 , 巩晨旭 , 陈烨荣 , 何星磊 , 赵彬 , 余春 , 叶克印 . 金属钴氟络合物催化酰氯/磺酰氯的氟化反应[J]. 化学学报, 2026 : 26080283 . DOI: 10.6023/A26080283

Abstract

Acyl fluorides are valuable intermediates in organic synthesis and have found broad applications in medicinal chemistry and functional materials. However, established synthetic methods often rely on unstable or hazardous fluorinating reagents, harsh reaction conditions, or expensive catalysts, thereby limiting their practical utility. Herein, we report an air-compatible fluorination of acyl chlorides and sulfonyl chlorides catalyzed by the cobalt fluoride complex [CoF3(terpy)]·MeOH·H2O (terpy = 2,2′:6′,2″-terpyridine), with inexpensive and readily available potassium fluoride (KF) serving as the terminal fluoride source. In a typical procedure, an oven-dried Schlenk tube equipped with a magnetic stir bar was charged with an acyl chloride or sulfonyl chloride (0.20 mmol), [CoF3(terpy)]·MeOH·H2O (0.010 mmol, 5.0 mol%), KF (0.40 mmol, 2.0 equiv.), and acetonitrile (2.0 mL). The mixture was stirred in air at 25 °C for 10 h. After completion of the reaction, the mixture was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography. Under the optimized conditions, benzoyl chloride was converted to benzoyl fluoride in 99% yield. Moreover, the catalytic system exhibited good reactivity and functional-group tolerance toward electronically and structurally diverse acyl and sulfonyl chlorides. Notably, it enabled the preparation of functional products, including a coumarin-derived fragrance and the fluorescent inhibitor dansyl fluoride. A gram-scale reaction conducted on a 5.0 mmol scale afforded 1.21 g of the target sulfonyl fluoride in 96% yield, demonstrating the preparative utility of the method. Density functional theory calculations indicated that fluoride transfer from the axial Co-F bond is kinetically favored over transfer from the equatorial Co-F bond, with calculated activation free energies of 23.2 and 26.9 kcal·mol⁻¹, respectively. Mulliken charge analysis further suggested that the axial fluoride ligand has greater nucleophilic character. Collectively, these results support a plausible catalytic pathway involving fluoride transfer from the axial Co-F bond to the carbonyl carbon of the acyl chloride, followed by regeneration of the cobalt fluoride catalyst by KF. Overall, this protocol features mild reaction conditions, operational simplicity, broad substrate scope, and good functional-group tolerance, providing a practical and economical route to acyl fluorides and sulfonyl fluorides.

Key words： cobalt fluoride complex; acyl fluoride; sulfonyl fluoride; fluorination; fluorine-chlorine exchange

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