Ligating Catalytically Active Peptides onto Microporous Polymers: A General Route Toward Specifically-Functional High Surface Area Platforms.

A versatile post-synthetic modification strategy to functionalize a high surface area microporous network (MPN-OH) by bio-orthogonal inverse electron-demand Diels-Alder (IEDDA) ligation is presented. While the polymer matrix is modified with a readily accessible norbornene isocyanate (Nor-NCO), a series of functional units presenting the robust asymmetric 1,2,4,5-tetrazine (Tz) allows easy functionalization of the MPN by chemoselective Nor/Tz ligation. A generic route is demonstrated, modulating the internal interfaces by introducing carboxylates, amides or amino acids as well as an oligopeptide d-Pro-Pro-Glu organocatalyst. The MPN-Pz-Peptide construct largely retains the catalytic activity and selectivity in an enantioselective enamine catalysis, demonstrates remarkable availability in different solvents, offers heterogeneous organocatalysis in bulk and shows stability in recycling settings.