金属-光协同催化的C(sp3)—C(sp3)还原偶联

doi:10.6023/cjoc202603047

有机化学 ›› 2026, Vol. 46 ›› Issue (7): 2589-2603.DOI: 10.6023/cjoc202603047 上一篇下一篇

综述与进展

金属-光协同催化的C(sp³)—C(sp³)还原偶联

郑湧龙^†, 罗鑫龙^†, 徐裕敏, 霍浩华^*()

厦门大学化学化工学院福建厦门 361005

收稿日期:2026-03-31 修回日期:2026-05-10 发布日期:2026-06-10
作者简介:
†共同第一作者
基金资助:
国家重点研发计划(2023YFA1507202); 国家重点研发计划(2021YFA1502500); 国家自然科学基金(22471228)

Metal/Photoredox-Catalyzed C(sp³)—C(sp³) Cross-Electrophile Coupling

Yonglong Zheng^†, Xinlong Luo^†, Yumin Xu, Haohua Huo^*()

College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005

Received:2026-03-31 Revised:2026-05-10 Published:2026-06-10
Contact: *E-mail: hhuo@xmu.edu.cn
About author:
†(The authors contributed equally to this work).
Supported by:
National Key R&D Program of China(2023YFA1507202); National Key R&D Program of China(2021YFA1502500); National Natural Science Foundation of China(22471228)

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摘要/Abstract

金属光氧化还原催化的C(sp³)—C(sp³)交叉亲电偶联反应(XEC)已成为构建药物、天然产物及生物活性分子中普遍存在的富含sp³碳中心分子骨架的重要策略. 该类方法通过整合光氧化还原催化与地球丰产金属催化, 能够在温和条件下直接利用丰富的亲电试剂构筑C(sp³)—C(sp³)键, 避免了敏感的有机金属试剂的使用. 系统综述了金属光氧化还原催化的C(sp³)—C(sp³)交叉亲电偶联反应的最新研究进展, 重点聚焦于镍、钴、铜和铁催化体系, 深入剖析了反应机理、设计原理、底物适用范围及新兴应用领域, 特别关注立体化学控制与官能团兼容性. 当前, 该领域仍面临诸多挑战, 包括还原剂种类有限、对映选择性反应体系尚处于起步阶段, 以及非镍基廉价金属催化潜力挖掘不足等. 此综述旨在为读者提供对该领域研究现状的全面认识, 并展望金属光氧化还原催化的C(sp³)—C(sp³)交叉亲电偶联反应在复杂分子合成中的应用范围与发展方向.

关键词: 金属-光协同催化, 交叉亲电偶联(XEC), C(sp³)—C(sp³)偶联

Cooperative base metal- and photoredox-catalyzed C(sp³)—C(sp³) cross-electrophile coupling (XEC) has emerged as a powerful strategy for the construction of sp³-rich molecular architectures prevalent in pharmaceuticals, natural products, and bioactive compounds. By integrating photoredox and base metal catalysis, these methods enable direct C(sp³)—C(sp³) bond formation from abundant electrophilic precursors under mild conditions, circumventing the need for sensitive organometallic reagents. This review comprehensively surveys recent advances in metal/photoredox-catalyzed C(sp³)—C(sp³) XECs, focusing on nickel-, cobalt-, copper-, and iron-catalyzed systems. Mechanistic insights, reaction design principles, substrate scopes, and emerging applications are critically analyzed, with particular attention paid to stereochemical control and functional group tolerance. Persistent challenges include limited reductant diversity, the nascent development of enantioselective variants, and the underexplored potential of non-nickel base metals. This review provides a detailed understanding of the current landscape and outlines future directions to expand the synthetic utility of C(sp³)—C(sp³) XEC in complex molecule synthesis.

Key words: metal/photoredox catalysis, cross-electrophile coupling (XEC), C(sp³)—C(sp³) coupling

引用此文

郑湧龙, 罗鑫龙, 徐裕敏, 霍浩华. 金属-光协同催化的C(sp³)—C(sp³)还原偶联[J]. 有机化学, 2026, 46(7): 2589-2603.

Yonglong Zheng, Xinlong Luo, Yumin Xu, Haohua Huo. Metal/Photoredox-Catalyzed C(sp³)—C(sp³) Cross-Electrophile Coupling[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2589-2603.

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图/表 13

Figure 1. Cooperative base metal- and photoredox-catalyzed C(sp3)—C(sp3) cross-electrophile coupling

Scheme 1. Ni/photoredox-catalyzed C(sp3)—C(sp3) XEC of aliphatic bromides

Scheme 2. Ni/photoredox-catalyzed C(sp3)—C(sp3) XEC of aliphatic alcohol derivatives via β-scission

Scheme 3. Ni/photoredox-catalyzed C(sp3)—C(sp3) XEC of N-alkylpyridinium salts with alkyl halides

Scheme 4. Ni/photoredox-catalyzed C(sp3)—C(sp3) XEC of glycosyl halides with NHPI esters or pyridinium salts

Scheme 5. Ni/photoredox-catalyzed C(sp3)—C(sp3) XEC enables the synthesis of alkyl cyclopropanes

Scheme 6. Ni/photoredox-catalyzed C(sp3)—C(sp3) XEC of α-silylated alkyl bromides with allylic sulfones

Scheme 7. Ni/photoredox-catalyzed enantioselective C(sp3)—C(sp3) XEC of alkyl halides with α-chloroboronates

Scheme 8. Co/photoredox-catalyzed C(sp3)—C(sp3) reductive coupling of two distinct alkenes

Scheme 9. Cu/photoredox-catalyzed C(sp3)—C(sp3) XEC of alkyl bromides with sulfonium salts

Scheme 10. Cu/photoredox-catalyzed C(sp3)—C(sp3) XEC of alkyl bromides with NHPI esters

Scheme 11. Fe/photoredox-catalyzed C(sp3)—C(sp3) XEC of NHPI esters with alkyl bromides

Scheme 12. Fe/photoredox-catalyzed C(sp3)—C(sp3) XEC for the formation of all-carbon quaternary centers

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金属-光协同催化的C(sp³)—C(sp³)还原偶联

Metal/Photoredox-Catalyzed C(sp³)—C(sp³) Cross-Electrophile Coupling

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