Citation: Nana Ma, Qiongjin Wang, Die Zhao, Bowen Duan, Dihao Kang, Shujun Li. Mechanistic insights into copper-mediated dehydroboration of alkane C(sp³)-H bonds: Triple roles of CuCl₂[J]. Chinese Chemical Letters, ;2026, 37(11): 112356. doi: 10.1016/j.cclet.2025.112356 shu

Mechanistic insights into copper-mediated dehydroboration of alkane C(sp³)-H bonds: Triple roles of CuCl₂

School of Chemistry and Chemical Engineering, Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, NMPA Key Laboratory for Research and Evaluation of Innovative Drug, Henan Normal University, Xinxiang 453007, China

mann076@htu.edu.cn

lisj@htu.edu.cn

Received Date: 27 October 2025
Revised Date: 22 December 2025
Accepted Date: 30 December 2025
Available Online: 2 January 2026

Figures(7)

This study elucidates the mechanism of copper-catalyzed C(sp³)–H borylation through density functional theory (DFT) calculations. We reveal the triple catalytic role of CuCl₂, which acts as a catalyst for hydrolytic cleavage of B₂cat₂, a photosensitize generating reactive chlorine radicals (Cl^•), and a dehydrating agent that facilitates the condensation of HOBcat intermediates to regenerate the active borylation species O(Bcat)₂. Key mechanistic insights include the dominance of Cl^• in hydrogen atom transfer (HAT), where direct hydrogen abstraction by Cl^• exhibits significantly lower activation barriers compared to alternative pathways involving preformed chlororadical-borate complexes. Computational analysis also identifies steric effects, rather than bond dissociation energy (BDE) trends, as the origin of primary C–H selectivity, with bulky intermediates preferentially accessing sterically accessible sites. These findings challenge conventional mechanistic assumptions and establish a unified framework for radical-mediated C–H functionalization, offering strategic principles for designing regioselective, atom-economical catalytic systems.
- Borylation,
- Copper-catalyzed,
- Density functional theory,
- Hydrogen atom transfer,
- Photoexcitation
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沈阳化工大学材料科学与工程学院沈阳 110142

Mechanistic insights into copper-mediated dehydroboration of alkane C(sp3)-H bonds: Triple roles of CuCl2

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通讯作者: 陈斌, bchen63@163.com

Mechanistic insights into copper-mediated dehydroboration of alkane C(sp³)-H bonds: Triple roles of CuCl₂