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DOI: 10.1055/a-2601-5489
Enantioselective Radical Acyl-Trifluoromethylation of Olefins
Enantioselective Acyl-Trifluoromethylation of Olefins by Bulky Thiazolium Carbene Catalysis.
Nat. Commun. 2025;
16: 3293
DOI: 10.1038/s41467-025-58423-z
Keywords
α-chiral β-fluoroalkylated ketones - asymmetric radical acyl-trifluoromethylation - thiazolium carbenes
Significance
Cramer and co-workers disclose the asymmetric acyl-trifluoromethylation of olefins using a thiazolium carbene as catalyst. The α-chiral β-fluoroalkylated ketones are obtained in moderate to very good yield (46–82 %) and with good to excellent enantioselectivity (91:9 to 98:2 er). The replacement of Togni’s reagent (3) by a modified hypervalent iodine reagent enables the introduction of diverse fluoroalkyl groups in the β-position. This facilitates access to a broad range of valuable, enantioenriched α-chiral β-fluoroalkyl ketones.
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Comment
Previous reports on N-heterocyclic carbene (NHC)-catalyzed acyl-fluoroalkylation of olefins established racemic and asymmetric routes up to 60:40 er. Nevertheless, a highly enantioselective reaction remained elusive. Starting from a reported, asymmetric variant of the best-performing achiral catalyst, Cramer and co-workers show how the optimization of electronic and steric parameters can be synergistically combined to yield a highly enantioselective NHC-based catalyst that can convert simple, unactivated olefins as well as pharmaceutical derivatives.
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Publication History
Article published online:
23 June 2025
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