Defective polyoxometalate-based MOFs enable one-pot two-step tandem catalysis: Direct conversion of alkenes to amino alcohols

The conventional synthesis of fine chemicals through multi-step independent reactions frequently necessitates intermittent catalyst substitution and laborious intermediate purification, posing significant challenges to process efficiency and energy sustainability. Herein, we developed a polyoxometalate (POM)-mediated defect engineering strategy to construct a spatially isolated but functionally coupled oxidation–amination dual-active sites by confining H₅PV₂Mo₁₀O₄₀ ({PV₂Mo₁₀}) in UiO-66 ({PV₂Mo₁₀}-0.1@UiO-66), achieving a one-pot two-step tandem conversion of alkenes to amino alcohols. The complete conversion process begins with {PV₂Mo₁₀}-catalyzed highly selective epoxidation of the alkenes (step A), followed by the in situ ring-opening amination of the epoxide intermediate by direct addition of the amine under the catalysis of the defective sites on UiO-66, without catalyst replacement and intermediate separation. Spectroscopic and catalytic performance analysis confirmed that the {PV₂Mo₁₀}-0.1@UiO-66 with dual-active sites has continuous reaction and multi-cycle structural stability. Based on the rich functionality of POMs and metal–organic frameworks (MOFs), their diverse assembly will provide a modular design platform for catalyst design aimed at tandem reactions.