Mandal, Tirtha and Ghosh, Mangish and Paps, Hendrik and Mandal, Tanumoy and Reiser, Oliver (2025) A general photocatalytic platform for the regio- and stereoselective β-chloroacylation of alkenes and alkynes using a heteroleptic copper(I) complex. NATURE CATALYSIS, 8 (6). ISSN 2520-1158,
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Atom transfer radical addition (ATRA) of aroyl chlorides to access beta-chloroacyl derivatives via photoredox catalysis remains hamstrung by the need to use precious iridium photocatalysts and activated alkenes as acceptors. Here we report a unified platform for the regioselective chlorocarbonylation of alkenes via visible-light-mediated ATRA of aroyl chlorides catalysed by a heteroleptic Cu(I) complex featuring extensive substrate scope, scalability and functional group tolerance. In addition, alkynes are amenable substrates, allowing E-selective beta-chlorovinyl ketone formation. The synthetic utility of the protocol is demonstrated through the functionalization of complex substrates, post-modifications of the products and the formal synthesis of pharmacologically relevant haloperidol, seratrodast and the naturally occurring piperidine alkaloid (-)-sedamine. This study undergirds the exclusive role of a heteroleptic copper(I) complex, which outperforms homoleptic copper(I) complexes-efficient for many ATRA processes-owing to its longer excited-state lifetime and adaptive ligand environment being tailored for the distinctive mechanistic steps catalysed by Cu(I) and Cu(II) in the title reaction.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | IRIDIUM-CATALYZED ADDITION; TRANSFER RADICAL-ADDITION; FRIEDEL-CRAFTS ACYLATION; CU-BASED SENSITIZERS; ACID-CHLORIDES; ATOM-TRANSFER; ENANTIOSELECTIVE SYNTHESIS; CHLOROVINYL KETONES; AROYL CHLORIDES; LIGHT; |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Oliver Reiser |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 09 Apr 2026 06:23 |
| Last Modified: | 09 Apr 2026 06:23 |
| URI: | https://pred.uni-regensburg.de/id/eprint/65877 |
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