This review highlights the recent applications of chiral N-tert-butanesulfinyl imines and chiral diene ligands, with bicyclo[3.3.0]octadiene and dicyclopentadiene skeletons, in asymmetric chemical transformations. The chiral sulfinamide–olefin products from allylation of N-tert-butanesulfinyl imines can be used as hybrid ligands for transition metal-catalyzed asymmetric reactions. The efforts in the further exploration of chiral sulfur–olefin ligands are also discussed.