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. 2025 Apr 11;27(14):3667-3672.
doi: 10.1021/acs.orglett.5c00780. Epub 2025 Apr 1.

Application of Lead-Free Metal Halide Perovskite Heterojunctions for the Carbohalogenation of C-C Multiple Bonds

Camilla Callegari  1 , Costanza Tedesco  2 , Alessia Corbo  1 , Mirko Prato  3 , Lorenzo Malavasi  2 , Davide Ravelli  1
Affiliations

Application of Lead-Free Metal Halide Perovskite Heterojunctions for the Carbohalogenation of C-C Multiple Bonds

Camilla Callegari et al. Org Lett. .

Abstract

A graphitic carbon nitride/lead-free double perovskite heterojunction (g-C3N4/Cs2AgBiCl6) has been adopted as a heterogeneous photocatalyst under visible light irradiation. The employed material enabled the atom transfer radical addition-type carbohalogenation of multiple C-C bonds, including (internal) alkenes and alkynes, with alkyl halides. The protocol showed a remarkable functional group tolerance, compatible with the late-stage functionalization of natural and pharmaceutical derivatives, and could be easily scaled up, delivering >1 g of the desired products.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. ATRA-Type Reactivity to Trigger the 1,2-Carbohalogenation of Alkenes with Alkyl Halides: (a) Typical Reaction Conditions, (b) Known Manifolds via Heterogeneous Photocatalysis, and (c) This Work
Figure 1
Figure 1
(a) Catalysts (CAT) employed in the present work. (b) Screening of selected conditions for the model ATRA-type reaction between 4-pentenyl benzoate (1a) and bromotrichloromethane (2a); NMR yields are reported (see general procedure GP-a in section 3.1 of the Supporting Information for further details). tr, traces; nd, not detected.
Scheme 2
Scheme 2. Mechanistic Considerations
Experiments supporting a radical pathway. Simplified mechanistic scenario for the photocatalyzed ATRA-type carbohalogenation of alkenes and alkynes.
See this image and copyright information in PMC

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