From Immobilization to Catalyst Use: A Complete Continuous‐Flow Approach Towards the Use of Immobilized Organocatalysts

The combination of chiral supported‐organocatalysts and flow chemistry promotes the sustainable production of enantioenriched compounds providing a very powerful tool for chemical and pharmaceutical industries. However, the rapid deactivation of these catalysts in heterogeneous asymmetric reactions has been limiting the expansion of the area. In this work we report for the first time the advantages of synthesizing, immobilizing, and using a silica‐supported organocatalyst under a complete continuous‐flow approach, showing the impact of this method on the morphology, structure and lifetime of the organocatalyst. The first generation MacMillan's organocatalyst was prepared from L‐phenylalanine and immobilized in silica through a carbamate linkage under batch and continuous‐flow conditions. We also evaluated the performance of both batch and continuous‐flow organocatalysts in the Diels‐Alder reaction for proof of concept. Flow to prevent degradation: A major issue of silica‐supported organocatalysts is the degradation of the solid material and the erosion of the matrix properties during its immobilization and usage in batch. In this work, we report for the first time, the advantages of a complete continuous‐flow approach towards the synthesis, immobilization and use of MacMillan's silica‐supported organocatalyst.