Citation: Xue Du, Ze-Hua Sun, Penglei Zhang, Li-Ping Xu, Xiaodong Xiong. Asymmetric chloro– and selenocyclization of 2-alkenyl anilides enabled by tertiary ammonium salt catalysis[J]. Chinese Chemical Letters, ;2026, 37(4): 111259. doi: 10.1016/j.cclet.2025.111259 shu

Asymmetric chloro– and selenocyclization of 2-alkenyl anilides enabled by tertiary ammonium salt catalysis

Xue Du ^{a, 1} ,
Ze-Hua Sun ^{c, 1} ,
Penglei Zhang ^a ,
Li-Ping Xu ^{b, *,} ,
Xiaodong Xiong ^{a, *,}

a.
School of Pharmacy, Nanchang University, Nanchang 330006, China
b.
School of Chemistry and Chemical Engineering, Shandong University, Ji’nan 250100, China
c.
School of Chemistry and Chemical Engineering, Shandong University of Technology, Zibo 255000, China

xulp@sdu.edu.cn

xiongxd@ncu.edu.cn

Received Date: 20 February 2025
Revised Date: 14 April 2025
Accepted Date: 24 April 2025
Available Online: 25 April 2025

Figures(7)

Available online-The enantioselective chlorination is a continuing challenge owing to the highly reactive nature of chloronium ions. Herein, tertiary ammonium salt catalysis for asymmetric chloro– and selenocyclization of 2-alkenyl anilides with high enantioselectivities were achieved at room temperature. This approach affords the green and atom-economical access to chiral 4H-3,1-benzoxazines with excellent functional-group tolerance. The catalyst could be reused for 3 runs, no obvious loss in catalytic activity and enantioselectivity was observed. This catalytic system can be applied to late-stage modification of pharmaceuticals and natural products. Computational mechanistic studies revealed that the non-classical hydrogen bond (C-H^…O) between the phosphate anion and ammonium cation plays crucial role in the stereocontrol of the reaction.
- Chlorination,
- Asymmetric synthesis,
- Phase-transfer catalysis,
- Tertiary ammonium salt,
- Organocatalysis
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