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Highly Efficient Cyclic Dinucleotide Based Artificial Metalloribozymes for Enantioselective Friedel–Crafts Reactions in Water
Author(s) -
Wang Changhao,
Hao Min,
Qi Qianqian,
Dang Jingshuang,
Dong Xingchen,
Lv Shuting,
Xiong Ling,
Gao Huanhuan,
Jia Guoqing,
Chen Yashao,
Hartig Jörg S.,
Li Can
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201912962
Subject(s) - enantioselective synthesis , chemistry , catalysis , dimer , friedel–crafts reaction , combinatorial chemistry , nucleic acid , aqueous solution , reactivity (psychology) , stereochemistry , organic chemistry , medicine , biochemistry , alternative medicine , pathology
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 Cu 2+ ions assemble into an artificial metalloribozyme (c‐di‐AMP⋅Cu 2+ ) 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⋅Cu 2+ gives rise to a 20‐fold rate acceleration compared to Cu 2+ ions. Based on various biophysical techniques and density function theory (DFT) calculations, a fine coordination structure of c‐di‐AMP⋅Cu 2+ metalloribozyme is suggested in which two c‐di‐AMP form a dimer scaffold and the Cu 2+ ion is located in the center of an adenine‐adenine plane through binding to two N7 nitrogen atoms and one phosphate oxygen atom.