Diastereoselective Synthesis of Tetrasubstituted Olefins from Internal Alkynes via Three‐Component Reaction Using a Heterogeneous Organometallic Triptycene‐Based Porous Palladium Catalyst

Abstract In this work, we report the design, synthesis, and application of a hyper‐crosslinked heterogeneous organometallic porous organic polymer (Pd@TP‐DPPF) catalyst for the efficient and sustainable dicarbofunctionalization of internal alkynes via a facile three‐component reaction. This strategy enables the highly trans ‐selective syntheses of tetrasubstituted olefins in excellent yields. The catalyst is constructed by integrating triptycene (TP) and 1,1′‐bis(diphenylphosphino)ferrocene (DPPF) into a robust palladium‐based porous framework, resulting in a unique heterogeneous system that efficiently mediates the coupling of internal alkynes with readily available iodoarenes and aryl/methyl boronic acids. This methodology also offers a versatile strategy for the syntheses of complex and valuable trans ‐selective alkenylsilanes under mild conditions, with high atom economy. Mechanistic studies support a trans ‐selective transformation pathway facilitated by the cooperative role of the polymer support and the palladium center. Importantly, the Pd@TP‐DPPF catalyst exhibits excellent recyclability, air/moisture stability, and operational simplicity, making it highly suitable for large‐scale and environmentally conscious synthetic applications. This work not only addresses a long‐standing challenge in the synthesis of highly substituted olefins but also exemplifies the principles of green chemistry through catalyst reusability, waste minimization, and efficient multicomponent transformation.