Hybrid Palladium-Catalyzed Intramolecular Carboamination of Conjugated Dienes: Synthesis of Functionalized Pyrrolidines via Selective Trifluoromethylarene Defluorination

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 7790 - 7794

Published: May 29, 2024

The incorporation of difluoromethylene groups into aza-heterocycles represents a compelling yet underexplored avenue in contemporary chemical research. In this study, we unveil hybrid palladium-catalyzed intramolecular gem-difluoroalkylamination conjugated dienes, providing versatile approach to the synthesis diverse functionalized pyrrolidines. Noteworthy features include mild reaction conditions and remarkable tolerance toward various functional groups. Additionally, use alkyl iodides as electrophiles facilitates generation corresponding alkylamination products. Control experiments support proposed radical–polar crossover pathway, offering insights underlying processes governing transformation.

Language: Английский

Visible-Light-Driven Palladium-Catalyzed 1,4-Difluoromethylative Functionalization of Conjugated Dienes Using Freon-22

Published: Feb. 19, 2024

We unveil a novel strategy that leverages cost-effective fluorine-containing sources for rapid synthesis of fluorinated com-pounds through multicomponent reactions. Our study introduces visible light-driven palladium-catalyzed 1,4-difluoromethyl difunctionalization conjugated dienes, capitalizing on the abundant industrial resource chlorodifluoro-methane (ClCF2H, Freon-22). Illuminated by blue LED light, palladium catalyst orchestrates efficient single electron reduction Freon-22's C-Cl bond, yielding CF2H radicals. This versatile protocol accommodates an extensive array amines, sulfinates, and enolates as nucleophiles, delivering regioselective products via SN2' substitution allylic intermediate. Redox-neutral in nature, this transformation finds utility late-stage functionalization drug molecules, while broad compatibility with diverse functional groups dienes underscores its versa-tility. Initial insights suggest involvement difluoromethyl radical intermediate, unveiling direct mild avenue to harness radicals from Freon-22.

Language: Английский

Pd-Catalyzed 1,4-Difluoromethylative Functionalization of 1,3-Dienes Using Freon-22

Organic Letters, Journal Year: 2024, Volume and Issue: 26(42), P. 9091 - 9096

Published: Oct. 15, 2024

We report a visible-light-driven, palladium-catalyzed 1,4-difluoromethylative functionalization of conjugated dienes using chlorodifluoromethane (ClCF

Language: Английский