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

doi:10.6023/cjoc202603047

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (7): 2589-2603.DOI: 10.6023/cjoc202603047 Previous Articles Next Articles

REVIEW

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)

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

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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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Fig. & Tab. 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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Fig. & Tab. 13

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金属-光协同催化的C(sp3)—C(sp3)还原偶联