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An enantioselective C-H functioffalization route to perfluoroalkyl-containing 3-azabicyclo[3.1.0]-hexanes is disclosed. A modular and bench-stable diazaphospholane ligand enables highly enantioselective Pd(0)-catalyzed cyclopropane C-H functionalization using trifluoroacetimidoyl chlorides as electrophilic partners. In turn, the resulting cyclic ketimine products react smoothly with a broad variety of nudeophiles in one-pot processes enabling the rapid and modular construction of heavily substituted pyrrolidines.