Iron-Catalyzed Reductive Ring Opening/<i>gem</i>-Difluoroallylation of Cyclopropyl Ketones
Bing Yuan, Chang Zhang, Haiyan Dong, Chuan Wang
Abstract
By merging C–C and C–F bond cleavage, we developed a regioselective ring opening/ gem -difluoroallylation of cyclopropyl ketones with α-trifluoromethylstyrenes, which proceeds under the catalysis of iron with the combination of manganese and TMSCl as the reducing agents, providing a new entry to the synthesis of carbonyl-containing gem -difluoroalkenes. Remarkably, the ketyl radical-induced selective C–C bond cleavage and the following generation of more-stable carbon-centered radicals enable complete regiocontrol of this ring opening reaction for various substitution patterns of the cyclopropane ring.
Topics & Concepts
ChemistryRegioselectivityCyclopropaneKetylRing (chemistry)CatalysisBond cleavageRadicalCleavage (geology)ManganeseMedicinal chemistryStereochemistryCombinatorial chemistryOrganic chemistryFracture (geology)EngineeringGeotechnical engineeringCyclopropane Reaction MechanismsFluorine in Organic ChemistryCatalytic C–H Functionalization Methods