Interlayer Immobilization of L-Proline in Mg–Al Layered Double Hydroxides for Efficient and Selective Aldol Condensation of Furfural with Ketones Under Mild Conditions

The homogeneous nature of L-proline organocatalysts restricts their application in aldol condensation due to poor recyclability and stability. Herein, L-proline was heterogenized by ionic intercalation into Mg–Al layered double hydroxides (LDHs), yielding a series of proline-intercalated catalysts with tunable layer structures. Co-precipitation and memory-effect reconstruction strategies were employed to regulate interlayer spacing and proline loading. The resulting catalysts exhibited efficient performance in the aldol condensation of furfural with ketones under mild conditions. The reconstructed catalyst re-Mg4Al1P achieved a furfural conversion of 88.67% and a total product yield of 85.54% at room temperature, with product selectivity exceeding 95%. Structural characterizations confirmed that proline was stabilized within the LDH interlayers via R–COO—Mg electrostatic interaction while preserving the secondary amine active site. Mechanistic analysis indicated that the reaction proceeded through enamine- or enol-mediated pathways depending on water content, while the layered LDH framework imposed geometric confinement that suppressed side reactions. Catalyst deactivation in aqueous systems was mainly attributed to proline leaching rather than structural collapse.