Study on the fluorination of α-carbonyl C<sub>sp3</sub>-Br bond catalyzed by Ph<sub>4</sub>PBr

WEI Fazheng; SONG Linpeng; LIU Xincheng; YOU Jun; LI Sida; LIU Jialin; WU Wenju; YU Yanchao

doi:10.11949/0438-1157.20260282

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Study on the fluorination of α-carbonyl C_sp3-Br bond catalyzed by Ph₄PBr

更新时间：2026-05-12

- Study on the fluorination of α-carbonyl C_sp3-Br bond catalyzed by Ph₄PBr
- CIESC Journal (2026)
- 作者机构：
  
  哈尔滨理工大学材料科学与化学工程学院黑龙江省绿色化工技术重点实验室，哈尔滨 150080
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260282
  CLC： O621.3
- Received：04 March 2026，
  
  Revised：2026-05-11，
  
  Accepted：12 May 2026，
- 稿件说明：
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WEI Fazheng, SONG Linpeng, LIU Xincheng, et al. Study on the fluorination of α-carbonyl C_sp3-Br bond catalyzed by Ph₄PBr[J/OL]. CIESC Journal, 2026. DOI: 10.11949/0438-1157.20260282.
DOI：

WEI Fazheng, SONG Linpeng, LIU Xincheng, et al. Study on the fluorination of α-carbonyl C_sp3-Br bond catalyzed by Ph₄PBr[J/OL]. CIESC Journal, 2026. DOI: 10.11949/0438-1157.20260282. DOI：

摘要

本文开发了一种以廉价四苯基溴化膦（Ph

PBr）为相转移催化剂、原位生成的Et₃N·2HF为氟源，实现羰基α-位C

sp³

-Br(Cl)键高效、高选择性氟化的新方法。该体系反应条件温和（40 ℃，6 h），操作简便，底物涵盖胺酰基α-位、芳香酮α-位、烷基酮CH

位及β-二酮CH

位等四类羰基α-溴代物，以60%–95%的收率获得相应α-氟代产物。该方法对芳香环上的C

sp2

-Br(Cl)键不影响，表现出优异的化学选择性，为含芳卤结构的复杂分子后期氟化修饰提供了便利。机理研究结果表明Ph

PBr可能是通过形成Ph

PF···H

···F

中间体增强氟亲核性、并经四元环过渡态实现氟取代的催化循环。该工作为有机氟化物的合成提供了一条经济、高效的新途径。

Abstract

In this paper

a new method for efficient and highly selective fluorination of C

sp³

-Br(Cl) bond at α-position of carbonyl group was developed by using cheap tetraphenylphosphonium bromide (Ph₄PBr) as phase transfer catalyst and in-situ generated Et₃N·2HF as fluorine source. The reaction conditions of this system are mild (40 ℃

6 h) and easy to operate. The substrates cover four types of carbonyl α-bromides

such as amide acyl α-position

aromatic ketone α-position

alkyl ketone CH

position and β-diketone CH

position

and the corresponding α-fluorinated products are obtained in 60% -95% yields. This method has no effect on the C

sp²

-Br(Cl) bond on the aromatic ring and exhibits excellent chemical selectivity

which facilitates the post-fluorination modification of complex molecules containing aromatic halogen structures. The mechanism research results show that Ph

PBr may enhance the fluorine nucleophilicity by forming Ph

PF···H

···F

intermediate and realize the catalytic cycle of fluorine substitution through the quaternary ring transition state. This work provides an economical and efficient new way for the synthesis of organic fluorides.

关键词

Keywords

references

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Study on the fluorination of α-carbonyl Csp3-Br bond catalyzed by Ph4PBr

DOI：10.11949/0438-1157.20260282

摘要

Abstract

关键词

Keywords

references

Study on the fluorination of α-carbonyl C_sp3-Br bond catalyzed by Ph₄PBr