The application of chiral hypervalent iodine reagents in asymmetric synthesis is highly desirable, as the reagents are metal-free, environmentally benign and employed under mild conditions. Three chiral diaryliodonium salts have been designed to provide chemoselectivity and asymmetric induction in asymmetric α-phenylation of carbonyl compounds. The synthetic routes to the selected targets are detailed herein, together with a structural investigation into the diastereoselectivity of the alkylation process.