有机化学 ›› 2024, Vol. 44 ›› Issue (6): 1733-1759.DOI: 10.6023/cjoc202401035 上一篇    下一篇

综述与进展

卤素原子转移(XAT)策略及应用新进展

蒋译锋a,b, 尹艳丽a,b,*(), 江智勇b,*()   

  1. a 河南工业大学前沿交叉科学与技术学院 河南郑州 450001
    b 河南师范大学化学化工学院 河南新乡 453007
  • 收稿日期:2024-01-29 修回日期:2024-02-06 发布日期:2024-02-27
  • 基金资助:
    国家自然科学基金(22171072); 国家自然科学基金(21925103)

Recent Advances in Strategies for Halide Atom Transfer (XAT) and Their Applications

Yifeng Jianga,b, Yanli Yina,b,*(), Zhiyong Jiangb,*()   

  1. a College of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou 450001
    b School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007
  • Received:2024-01-29 Revised:2024-02-06 Published:2024-02-27
  • Contact: * E-mail: yinzihust@163.com; 2018230@htu.edu.cn
  • Supported by:
    National Natural Science Foundation of China(22171072); National Natural Science Foundation of China(21925103)

随着自由基化学的发展, 对于具有较强键能且高氧化还原电位的烷基和芳基卤化物, 化学家们开发了一系列卤素原子转移(XAT)试剂. 这些试剂通过自由基取代途径攫取烷基和芳基的卤素原子, 并成功完成后续的官能团转化, 从而合成目标分子. 这些XAT试剂因其独特的反应性以及在有机合成中的多功能性而受到广泛关注. 近年来对于XAT试剂的综述主要集中于反应机理和种类的报道, 而对于其活化策略的研究较为有限. 基于此, 总结了近三年来关于XAT试剂的活化策略, 包括单电子转移、氢原子转移、能量转移和电子供体-受体(EDA)复合物四个方面进行阐述与讨论, 旨在弥补XAT试剂活化策略方面的研究空白, 为该领域提供新的理论支持和研究视角.

关键词: 卤素原子转移, 单电子转移, 氢原子转移, 能量转移, 电子供体-受体(EDA)复合物

Following the rapid advance of radical chemistry, a range of halogen atom transfer (XAT) reagents have been developed by chemists for alkyl and aryl halides, which typically feature strong bond strengths and high redox potentials. These reagents facilitate the extraction of halogen atoms from alkyl and aryl moieties via radical substitution pathways, thus generating radical species that undergo subsequent chemical transformations for the synthesis of valuable molecules. The unique reactivity and versatility of these XAT reagents have attracted much attention in organic synthesis. Recent reviews of XAT reagents have mainly focused on elucidating reaction mechanisms and classifying different types with limited exploration of activation strategies. In light of this, this paper provides a summary of the activation strategies for XAT reagents over the past three years. The discussion is organized into four aspects based on different strategies, namely single electron transfer, hydrogen atom transfer, energy transfer, and electron donor-acceptor (EDA) complexes. This review aims to address the research gaps in activation strategies of XAT reagents, providing new theoretical support and perspectives for the field.

Key words: halogen atom transfer, single electron transfer, hydrogen atom transfer, energy transfer, electron donor-acceptor (EDA) complex