This work describes an asymmetric intermolecular alkene aminoarylation using arylsulfinylamides as multifunctional all-in-one reagents featuring a traceless chiral auxiliary. The reaction tolerates a wide variety of N-atom donors and is compatible with both 1,2-disubstituted styrenes, vinyl amides and vinyl ethers, thus providing access to valuable ,-diarylethylamines, aryl-, -ethylenediamines and -aryl--aminoalcohols. Excellent levels of both relative and absolute stereocontrol are achieved in the two newly forged stereogenic centres, governed by the configuration of the chiral sulfoxide tether. Characterization of the reaction mechanism revealed an interesting dichotomy in the initiation of the photoredox catalytic cycle wherein either electron-rich alkenes or sulfinylamides are preferentially activated at the expense of the Ir photocatalyst.
