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Photoinduced Boryl Radical-Promoted Stepwise Dehalogenative Functionalization of Polyhaloalkyl Groups.

Created on 09 Sep 2026

Authors

Fang-Song Zhang, Zhi-Qiang Ding, Yan Liu, Jian-Ming Yang, Yuan Peng, Yee Lin Phang, Ji-Kang Jin, Feng-Lian Zhang, Tian Ye, Jialong Jie, Hongmei Su, Yi-Feng Wang

Published in

Angewandte Chemie (International ed. in English). Pages e6273159. Sep 08, 2026. Epub Sep 08, 2026.

Abstract

Partially halogenated alkyl motifs are prevalent in pharmaceuticals and functional materials, yet their synthesis via selective, stepwise dehalogenative functionalization of readily available polyhalogenated precursors constitutes a marked challenge. Furthermore, a general method capable of functionalizing C─F, C─Cl, and C─Br bonds under unified conditions has remained elusive because of their markedly different reactivities. Herein, we report a visible-light-driven, photocatalyst-free strategy for selective dehalogenative alkylation and hydrodehalogenation of polyhaloalkyl molecules across three C─X (X = F, Cl, or Br) bond types. The method relies on a unique photoactive complex formed from 4-dimethylaminopyridine (DMAP)-BH3 and thiophenol through synergistic noncovalent interactions. Visible-light excitation triggers a previously unrecognized thiol-to-borane charge transfer, ultimately generating the DMAP-boryl radical for selective C─X bond activation. The protocol accommodates tetra-, tri-, and dihaloalkyl substrates with broad functional group tolerance. Sequential C─X bond functionalization further provides modular access to structurally diverse partially halogenated alkyl architectures. Time-resolved spectroscopic studies and density functional theory (DFT) calculations support the proposed mechanistic pathway.

PMID:
42711735
Bibliographic data and abstract were imported from PubMed on 09 Sep 2026.

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