Photocatalytic C(sp2)—C(sp3) Cross-Coupling between C(sp2)—Cl Bond and C(sp3)—H Bond

doi:10.6023/cjoc202605031

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3640-3645.DOI: 10.6023/cjoc202605031 Previous Articles Next Articles

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光催化C(sp²)—Cl键与C(sp³)—H键的C(sp²)—C(sp³)交叉偶联

何晓君^a^,^b, 陈彬^a^,^b, 郭晓宁^a^,^b, 佟振合^a^,^b, 吴骊珠^a^,^b^,^*()

^a 中国科学院理化技术研究所超分子光化学实验室中国科学院-香港大学新材料合成和检测联合实验室新基石科学实验室北京 100190
^b 中国科学院大学未来技术学院北京 100049

收稿日期:2026-05-31 修回日期:2026-06-25 发布日期:2026-07-23
通讯作者: 吴骊珠
基金资助:
国家重点研发计划(2022YFA1503200); 国家重点研发计划(2021YFA1500100); 国家自然科学基金(22588101); 国家自然科学基金(22193013); 国家自然科学基金(22571310); 中国科学院战略性先导科技专项(XDB0960000); 中国科学院基础研究领域青年科学家项目(YSBR-142); 新基石科学基金会资助项目.

Photocatalytic C(sp²)—C(sp³) Cross-Coupling between C(sp²)—Cl Bond and C(sp³)—H Bond

Xiao-Jun He^a^,^b, Bin Chen^a^,^b, Xiao-Ning Guo^a^,^b, Chen-Ho Tung^a^,^b, Li-Zhu Wu^a^,^b^,^*()

^a Key Laboratory of Supramolecular Photochemistry, The University of Hong Kong-Chinese Academy of Sciences Joint Laboratory on New Materials, New Cornerstone Science Laboratory, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190
^b School of Future Technology, University of Chinese Academy of Sciences, Beijing, 100049

Received:2026-05-31 Revised:2026-06-25 Published:2026-07-23
Contact: Li-Zhu Wu
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Key R&D Program of China(2022YFA1503200); National Key R&D Program of China(2021YFA1500100); National Natural Science Foundation of China(22588101); National Natural Science Foundation of China(22193013); National Natural Science Foundation of China(22571310); Strategic Priority Research Program of the Chinese Academy of Science(XDB0960000); CAS Project for Young Scientists in Basic Research(YSBR-142); New Cornerstone Science Foundation.

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Abstract

Cross-coupling between C(sp²)—Cl bond and C(sp³)—H bond is an essential way to construct C(sp²)—C(sp³) bond. By merging photosensitizer and nickel catalyst, photocatalytic system proceeds the reactions under mild and efficient condition, which enriches the activation fashion of C(sp³)—H bond. It is commonly accepted that the reaction undergoes the catalytic cycle containing Ni(0) species. Herein, we report that when carbazole is utilized as a photosensitizer, Ni(I) rather than Ni(0) species is the primary nickel species in the system. The cooperation between carbazole photosensitizer and Ni(I) species exhibits competent catalytic ability to the cross-coupling of C(sp²)—Cl bond in aryl chloride and C(sp³)—H bond in good to excellent yields.

Key words: C(sp²)—C(sp³) cross-coupling, photosensitizer, nickel species at low valance state, photocatalysis

Cite this article

Xiao-Jun He, Bin Chen, Xiao-Ning Guo, Chen-Ho Tung, Li-Zhu Wu. Photocatalytic C(sp²)—C(sp³) Cross-Coupling between C(sp²)—Cl Bond and C(sp³)—H Bond[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3640-3645.

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Fig. & Tab. 6

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Entry	Variation from the standard conditions	Yield^b/%
1		93 (98)
2	No 4CzIPN
3	No NiBr₂•DME
4	No L1
5	No NiBr₂•DME and L1
6	No K₃PO₄
7	Dark, r.t.
8	Dark, 80 ℃
9^c	THF (0.017 mol/L)	99
10^d	THF (0.05 mol/L)	73
11	Bpy instead of L1	43
12	K₂CO₃ instead of K₃PO₄	84
13	LiOMe instead of K₃PO₄
14^e	Ir and Ni(cod)₂ instead of 4CzIPN and NiBr₂• DME	90

Entry	Variation from the standard conditions	Yield^b/%
1		93 (98)
2	No 4CzIPN
3	No NiBr₂•DME
4	No L1
5	No NiBr₂•DME and L1
6	No K₃PO₄
7	Dark, r.t.
8	Dark, 80 ℃
9^c	THF (0.017 mol/L)	99
10^d	THF (0.05 mol/L)	73
11	Bpy instead of L1	43
12	K₂CO₃ instead of K₃PO₄	84
13	LiOMe instead of K₃PO₄
14^e	Ir and Ni(cod)₂ instead of 4CzIPN and NiBr₂• DME	90

Photocatalyst	E(P^＋/*P)/V	E(*P/P^－)/V	E(P^＋/P)/V	E(P/P^－)/V	λ_max/nm		E_0-0/eV
Photocatalyst	E(P^＋/*P)/V	E(*P/P^－)/V	E(P^＋/P)/V	E(P/P^－)/V	Excitation	Emission	E_0-0/eV
4CzIPN	－0.91	＋1.23	＋1.71	－1.39	450	519	2.62
Ir[dF(CF₃)ppy]₂(dtbbpy)PF₆	－1.02	＋1.44	＋1.69	－1.27	369	478	2.71

Photocatalyst	E(P^＋/*P)/V	E(*P/P^－)/V	E(P^＋/P)/V	E(P/P^－)/V	λ_max/nm		E_0-0/eV
Photocatalyst	E(P^＋/*P)/V	E(*P/P^－)/V	E(P^＋/P)/V	E(P/P^－)/V	Excitation	Emission	E_0-0/eV
4CzIPN	－0.91	＋1.23	＋1.71	－1.39	450	519	2.62
Ir[dF(CF₃)ppy]₂(dtbbpy)PF₆	－1.02	＋1.44	＋1.69	－1.27	369	478	2.71

Stock solution	Composition (in 8 mL of THF)
A	1.25×10^－4 mol/L 4CzIPN, 1.25×10^－3 mol/L NiBr₂• DME, 1.25×10^－3 mol/L L1, 21.2 mg K₃PO₄
B	1.25×10^－4 mol/L Ir[dF(CF₃)ppy]₂(dtbbpy)PF₆, 1.25×10^－3 mol/L NiBr₂•DME, 1.25×10^－3 mol/L L1, 21.2 mg K₃PO₄
C	1.25×10^－4 mol/L 4CzIPN, 1.25×10^－3 mol/L NiBr₂• DME, 1.25×10^－3 mol/L L1
D	1.25×10^－4 mol/L Ir[dF(CF₃)ppy]₂(dtbbpy)PF₆, 1.25×10^－3 mol/L NiBr₂•DME, 1.25×10^－3 mol/L L1

光催化C(sp²)—Cl键与C(sp³)—H键的C(sp²)—C(sp³)交叉偶联

Photocatalytic C(sp²)—C(sp³) Cross-Coupling between C(sp²)—Cl Bond and C(sp³)—H Bond

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