Chiral olefins as a lately emerging type of ligands are among the most promising ligands for asymmetric catalysis.1 With the aim of developing structurally new, effective, and accessible chiral olefin ligands, one class of chiral chain dienes with flexible frameworks and two terminal olefins as coordination groups have been successfully developed by our group and proven to be effective for transition-metal-catalyzed asymmetric reactions to achieve high levels of ee values.