Citation: Hong Xin, Shutao Wang, Li-Na Guo, Cheng Guan, Jinyi Liao, Zi-Hang Yuan, Zhengze Zhang, Xin-Hua Duan. An unusual carbon radical-mediated ring-opening/amination or esterification cascade of unstrained α-haloalkyl cycloketone derivatives[J]. Chinese Chemical Letters, ;2026, 37(7): 111939. doi: 10.1016/j.cclet.2025.111939 shu

An unusual carbon radical-mediated ring-opening/amination or esterification cascade of unstrained α-haloalkyl cycloketone derivatives

Hong Xin ^{a, 1} ,
Shutao Wang ^{a, 1} ,
Li-Na Guo ^a ,
Cheng Guan ^a ,
Jinyi Liao ^a ,
Zi-Hang Yuan ^a ,
Zhengze Zhang ^b ,
Xin-Hua Duan ^{a, b, *,}

a.
Department of Chemistry, School of Chemistry, Xi'an Key Laboratory of Sustainable Energy Material Chemistry and Engineering Research Center of Energy Storage, Materials and Devices, Ministry of Education Xi'an Jiaotong University, Xi'an 710049, China
b.
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China

duanxh@xjtu.edu.cn

Received Date: 22 May 2025
Revised Date: 25 September 2025
Accepted Date: 9 October 2025
Available Online: 10 October 2025

Figures(8)

The carbon-centered radical induced C‒C bond cleavage in strained cyclopropane is a well-known process. However, achieving similar transformations in unstrained rings is still challenging. Herein, a novel inexpensive Cu-catalyzed strategy for the carbon-centered radical-mediated ring-opening/amination or esterification cascade of unstrained α-haloalkyl cycloketone derivatives is presented. Differ from the classical Dowd-Beckwith ring expansion reaction, a ring opening cascade occurred successfully under a simple copper/base catalytic system, yielding useful distal unsaturated amides and esters in good to excellent yields. Mechanistic studies and DFT calculations indicate that the halogen-bonding interaction between halide and base is crucial for the activation of the C‒Br bond. Furthermore, the formation of a bicyclic Cu-complex via bi-dentate coordination, including O–Cu–^•CH₂, seems to be a crucial factor that promotes ring opening rather than the conventional ring expansion. This work would not only bring new vitality for the radical-mediated C‒C bond cleavage, but also highlight the potential of protocol for synthesizing bioactive molecules.
- Carbon radical-mediated,
- C-C bond cleavage,
- Amination,
- Esterification,
- Halogen bond
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