2 publications

2 publications

Highly Efficient Cyclic Dinucleotide Based Artificial Metalloribozymes for Enantioselective Friedel–Crafts Reactions in Water

Chen, Y.; Wang, C.

Angew. Chem. Int. Ed. 2020, 59, 3444-3449, 10.1002/anie.201912962

The diverse secondary structures of nucleic acids are emerging as attractive chiral scaffolds to construct artificial metalloenzymes (ArMs) for enantioselective catalysis. DNA‐based ArMs containing duplex and G‐quadruplex scaffolds have been widely investigated, yet RNA‐based ArMs are scarce. Here we report that a cyclic dinucleotide of c‐di‐AMP and Cu2+ ions assemble into an artificial metalloribozyme (c‐di‐AMP⋅Cu2+) that enables catalysis of enantioselective Friedel–Crafts reactions in aqueous media with high reactivity and excellent enantioselectivity of up to 97 % ee. The assembly of c‐di‐AMP⋅Cu2+ gives rise to a 20‐fold rate acceleration compared to Cu2+ ions. Based on various biophysical techniques and density function theory (DFT) calculations, a fine coordination structure of c‐di‐AMP⋅Cu2+ metalloribozyme is suggested in which two c‐di‐AMP form a dimer scaffold and the Cu2+ ion is located in the center of an adenine‐adenine plane through binding to two N7 nitrogen atoms and one phosphate oxygen atom.


Metal: Cu
Ligand type: RNA
Host protein: RNA
Anchoring strategy: Dative
Optimization: Chemical
Max TON: 20
ee: 97
PDB: ---
Notes: ---

Iron-porphyrin Catalyzed Carbene Transfer Reactions – an Evolution fro Biomimetic Catalysis towards Chemistry-inspired Non-natural Reactivities of Enzymes

Koenigs, R.M.; Weissenborn, M.J.

ChemCatChem 2020, 10.1002/cctc.201901565

Bioinspired, synthetic porphyrin complexes are important catalysts in organic synthesis and play a pivotal role in efficient carbene transfer reactions. The advances in this research area stimulated recent, “chemo‐inspired” developments in biocatalysis. Today, both synthetic iron complexes and enzymes play an important role to conduct carbene transfer reactions. The advances and potential developments in both research areas are discussed in this concept article.


Metal: Fe
Ligand type: Porphyrin
Host protein: ---
Anchoring strategy: ---
Optimization: Chemical & genetic
Reaction: Carbene insertion
Max TON: ---
ee: ---
PDB: ---
Notes: ---