Development of Immobilized Chiral Iridium Catalysts by Strengthening Coordination Bonds for Z‐retentive Asymmetric Allylic Substitution

Abstract Ir‐catalyzed asymmetric allyl substitution is pivotal for constructing chiral compounds. However, addressing Ir scarcity and developing sustainable catalysts for industrial applications remains a significant challenge. This study presents a polymer‐supported heterogeneous chiral single‐Ir‐site catalyst, wherein the coordination is optimized through modulation of anions, resulting in a significant reduction in metal leaching. The catalysts exhibit exceptional performance in terms of enhanced enantioselectivity and broad applicability in Z ‐retentive asymmetric allylic substitution reactions, even accommodating a wide range of diverse functional groups. Specifically, the catalyst demonstrates minimal metal leaching over 14 cycles, marking a notable improvement compared to previously reported catalysts. The practical optimization of this reaction highlights the potential application value of such catalysts, offering insights for the development of chiral heterogeneous catalysts.