<i>Z</i>‑Selective Dienylation Enables Stereodivergent Construction of Dienes and Unravels a Ligand-Driven Mechanistic Dichotomy

The development of stereoselective and efficient reactions for the construction of conjugated dienes and polyenes has remained at the forefront of organic chemistry, due to their key roles in medicinal chemistry, organic synthesis, and material science. The synthesis of conjugated dienes and polyenes is typically accomplished in a multistep manner by the sequential installation of individual CC bonds because it allows for control of stereoselectivity and efficiency of formation of each double bond. A conceptually distinct dienylation approach entails a stereoselective appendage of a four-carbon unit, shortcutting diene synthesis. Dienylation with sulfolene provided a direct route to E-dienes, but the synthesis of substantially more challenging Z-dienes remained elusive. Here, we report that a highly Z-selective dienylation can now be achieved by a simple adjustment of a ligand, enabling stereodivergent synthesis of E- and Z-dienes from one reagent and in one step. A detailed mechanistic investigation of the E- and Z-selective dienylation provided insight into the divergent behavior of the two catalytic systems and revealed that differences in relative stabilities of catalytically active palladium phosphine complexes have a major impact on the stereochemical outcomes of the dienylation.