H 4 )], [1] also known as the Zeise salt, in 1827, considerable numbers of olefin-coordinated transition-metal complexes have been synthesized for extensive use in organometallic and organic chemistry.[2]They also serve as useful precatalysts in the field of asymmetric catalysis. The labile olefins are rapidly and quantitatively replaced by optically active ligands that bear heteroatoms, such as nitrogen and phosphorus, which exhibit a stronger binding affinity towards metal atoms than the olefins, efficiently enabling the in situ generation of chiral catalysts.[3] However, the utilization of optically active olefin ligands as chiral modifiers had not received much attention until the independent studies of Hayashi et al. [4] and Carreira et al. [5] Their discoveries have demonstrated that chiral dienes with the appropriate geometry can form reasonably stable metal complexes due to chelation effects. These chiral diene-metal catalysts, particularly the rhodium complexes, have since been tested in catalytic asymmetric carboncarbon bond-forming reactions and were found to exhibit higher catalytic activities and enantioselectivities than phosphine ligands.[6] Since then, the design, synthesis, and investigation of chiral dienes for a wide range of asymmetric transformations has attracted much attention among synthetic organic chemists. [7, 8]