Abstract
The diverse structures of nucleic acids as scaffolds have brought the significant advancement for DNA‐based enantioselective catalysis, yet RNA‐based enantioselective catalysis is lacking investigation. Herein, we report a small, natural RNA of cyclic di‐AMP (c‐di‐AMP) and Cu2+ ions assemble into an artificial metalloribozyme (c‐di‐AMP·Cu2+), that could effectively catalyze the enantioselective Diels–Alder reactions with up to 80 % ee. The enantioselective catalytic performance of c‐di‐AMP·Cu2+ has been studied by thorough investigations of different metal cofactors, c‐di‐AMP/Cu2+ molar ratios, additives, buffers and c‐di‐AMP analogues. In addition, the assembly of c‐di‐AMP·Cu2+ gives rise to 300‐fold and 5‐fold rate acceleration compared to the uncatalyzed reaction and Cu2+ ions, respectively. This work provides a simple and efficient strategy to construct the RNA‐based catalysts that would expand the current nucleic acids‐based catalysis and might hint the possible catalytic RNA in primordial chemistry.
Published Version
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