The diastereoselective radical addition of tertiary amines to electron defi
cient alkenes as well as the radical tandem reaction of aniline derivatives
with a chiral alkene have been carried out. The products were isolated wit
h yields up to 94% and high facial diastereoselectivity (> 95%). The effici
ency of the reactions have been achieved by using electron donor substitute
d aromatic ketones as sensitizers in a photochemical induced electron trans
fer process. This step initiates the radical chain reaction.