Tandem Hydroformylation‐Aldol Condensation Reaction Enabled by Zn‐MOF‐74

Abstract The tandem hydroformylation‐aldol condensation (tandem HF‐AC) reaction offers an efficient synthetic route to the synthesis of industrially relevant products. The addition of Zn‐MOF‐74 to the cobalt‐catalyzed hydroformylation of 1‐hexene enables tandem HF‐AC under milder pressure and temperature conditions than the aldox process, where zinc salts are added to cobalt‐catalyzed hydroformylation reactions to promote aldol condensation. The yield of the aldol condensation products increases by up to 17 times compared to that of the homogeneous reaction without MOF and up to 5 times compared to the aldox catalytic system. Both Co 2 (CO) 8 and Zn‐MOF‐74 are required to significantly enhance the activity of the catalytic system. Density functional theory simulations and Fourier‐transform infrared experiments show that heptanal, the product of hydroformylation, adsorbs on the open metal site (OMS) of Zn‐MOF‐74, thereby increasing the electrophilic character of the carbonyl carbon atom and facilitating the condensation.