Copper-Catalyzed gem-Dichloroalkyl-Arylation of Unactivated Alkenes for the Synthesis of Dichloroalkyl-Azaheteropolycycles.

We report copper-catalyzed dichloroalkyl-arylation of terminal alkenes containing a pendant aryl group bearing trichloroalkyl compounds as radical precursors. Tandem radical cyclization proceeded with high regioselectivity, short reaction times, and tolerance for a broad array of functional groups and complex substrates, yielding fused azaheterocycles such as pyrrolizidines and indolizidines, which serve as important intermediates in total synthesis. This reaction sequence affords the installation of the gem-dichloroalkyl group, a potent pharmacophore and versatile building block in organic synthesis.