[reaction: see text] The addition of organoboronic acids to chiral sulfinimines proceeds under mild conditions at room temperature, using Rh(I) catalysis in the absence of external phosphine ligands. Clean reaction only occurs in the presence of water as a cosolvent. The sulfinamide adducts are formed with high diastereoselectivities, providing a convenient route to the synthesis of enantiomerically enriched chiral benzylic amines.