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

Area of Science:

• Materials Science
• Organic Chemistry
• Catalysis

Background:

• High surface area microporous networks (MPNs) offer potential for advanced applications.
• Post-synthetic modification is crucial for tailoring material properties.
• Bio-orthogonal reactions provide precise and efficient functionalization methods.

Purpose of the Study:

• To develop a versatile post-synthetic modification strategy for MPNs.
• To functionalize MPNs using bio-orthogonal inverse electron-demand Diels-Alder (IEDDA) ligation.
• To introduce diverse functionalities and assess their impact on catalytic performance.

Main Methods:

• Modification of a microporous network (MPN-OH) with norbornene isocyanate (Nor-NCO).
• Functionalization using asymmetric 1,2,4,5-tetrazine (Tz) derivatives via Nor/Tz ligation.
• Introduction of carboxylates, amides, amino acids, and an oligopeptide organocatalyst.

Main Results:

• Successful functionalization of MPNs via chemoselective Nor/Tz ligation.
• The MPN-Pz-Peptide construct retained catalytic activity and selectivity in enantioselective enamine catalysis.
• Demonstrated availability in various solvents and stability in recycling settings for heterogeneous organocatalysis.

Conclusions:

• The presented IEDDA ligation strategy is a versatile tool for functionalizing MPNs.
• This method enables the development of stable and recyclable heterogeneous organocatalysts.
• The functionalized MPNs show promise for advanced catalytic applications.