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Synlett 2024; 35(09): 1057-1061
DOI: 10.1055/a-2225-8858
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Chemical Synthesis and Catalysis in Germany

Chemoselective Vicinal Dichlorination of Alkenes by Iron Ligand-to-Metal Charge-Transfer Catalysis

Jessica Stahl‡
Faculty of Chemistry and Pharmacy, University of Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany
,
Thilo Reiter‡
Faculty of Chemistry and Pharmacy, University of Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany
,
Burkhard König∗
› Author AffiliationsThe work was supported by the DFG-funded Collaborative Research Center ‘Assembly Controlled Chemical Photocatalysis’ (TRR 325 – 444632635). J.S. thanks the Studienstiftung des Deutschen Volkes for a Ph.D. stipend.
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Abstract

We report the photocatalytic functionalization of terminal alkenes to vicinal dichlorides by using visible light and FeCl3 as a catalyst, LiCl as a chloride source, and air as an oxidant. The transformation is proposed to be initiated by ligand-to-metal charge-transfer bond homolysis of a Fe–Cl bond, giving a highly reactive chloride radical able to initiate the functionalization of olefins. The process shows high chemoselectivity and broad functional-group tolerance with yields of up to 94% under mild conditions.

Key words

iron catalysis - photocatalysis - ligand-to-metal charge transfer - chlorination - alkenes - vicinal dichlorides

Supporting Information



Publication History

Received: 26 October 2023

Accepted after revision: 11 December 2023

Accepted Manuscript online:
11 December 2023

Article published online:
18 January 2024

© 2024. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

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