A Bifunctional, Site-Isolated Metal-Organic Framework-Based Tandem Catalyst

Herein, we present the synthesis of a metalorganic framework-based tandem catalyst that contains two distinct catalytic domains. Zn(II)-based IRMOF-9-Irdcppy-NH2 (IRMOF = isoreticular metalorganic framework) has both organocatalytic amine and organometallic Ir(I) groups that were incorporated by both pre- and postsynthetic functionalization methods. The isolated amine and Ir(I) sites of IRMOF-9-Irdcppy-NH2 are shown to be independently catalytically active for performing a Knoevenagel condensation and allylic N-alkylation, respectively. More importantly, IRMOF-9-Irdcppy-NH2 can act as a tandem catalyst for both of these organic transformations in a one-pot reaction, which cannot be achieved efficiently using the combined, homogeneous analogues.