ConspectusTransition-metal-catalyzed coupling reactions of dienes (such as 1,3-dienes, alkoxyallenes, and aminoallenes) with carbon nucleophiles have proven to be a highly effective method for creating Csp3-Csp3 bonds. These reactions have perfect atom economy and typically occur under mild reaction conditions. By using chiral metal complexes as catalysts, it is possible to create enantioenriched molecules bearing allylic stereocenters with high enantioselectivities. However, challenges arise when Csp3-Csp3 bonds bearing two vicinal stereocenters are constructed through this type of coupling reaction. Due to the inherent diastereoselectivities, only the kinetically favored diastereoisomers (either the syn- or anti-product) are usually obtained through the transition-metal catalyst system. Achieving complementary stereoisomers with high selectivity, which require complete control of both absolute and relative configurations of multiple chiral centers in a single chemical transformation, is usually impossible.Over the past decade, significant advancements have been made in stereodivergent synthesis. Notably, iridium-related synergistic catalysis has been rapidly developed for stereodivergent allylic alkylation reactions. However, these systems were limited to using allylic alcohol derivatives as electrophilic partners. Finding ways to extend the use of synergistic catalysis to other types of stereodivergent reactions is a crucial issue that needs to be addressed.In 2019, we reported the first palladium-mediated synergistic system for the stereodivergent Csp3-Csp3 coupling between 1,3-dienes and aldimine esters. Lately, this strategy has proven successful in accessing stereodivergent coupling with diverse substrate patterns. In this Account, we will summarize our laboratory's efforts in developing a range of palladium-involved synergistic catalysis systems for the stereodivergent Csp3-Csp3 coupling reactions of dienes. We discovered several synergistic catalysis systems, including Pd/Cu(Ag), Pd/amine, Pd/Lewis base, and Pd/PTC. Additionally, we developed diverse dienes, such as 1,3-dienes, alkoxyallenes, and aminoallenes, to serve as suitable coupling partners for stereodivergent coupling. These processes provide an efficient method for constructing a range of chiral scaffolds bearing vicinal stereocenters. Density functional theory (DFT) calculations have been performed to elucidate the reaction mechanism and to rationalize the origins of the stereochemistry for some of the synergistic catalyst systems. Finally, the synthetic application of these methods has been demonstrated in the concise total synthesis of a number of natural products and bioactive molecules. It is anticipated that an increasing number of chemists will join in the research on stereodivergent Csp3-Csp3 coupling reactions and contribute to more elegant examples in this area. We believe future development will further push the boundary of asymmetric catalysis and find more innovative applications soon for synthesizing complex chiral molecules.