Highly Efficient Cyclic Dinucleotide Based Artificial Metalloribozymes for Enantioselective Friedel–Crafts Reactions in Water. (22nd January 2020)

• Record Type: Journal Article
• Authors: 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
• Is Part Of: Angewandte Chemie. Volume 132:Number 9(2020)
• Page Start: 3472
• Page End: 3477
• Publication Date: 2020-01-22
• Subjects: Künstliche Metalloribozyme -- c-di-AMP -- Cyclische Dinucleotide -- Homogene Katalyse -- Nukleinsäuren-basierte Katalyse; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201912962
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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. Abstract : Ein künstliches Metalloribozym auf der Basis eines zyklischen Dinukleotids, das aus c‐di‐AMP und Cu 2+ ‐Ionen zusammengesetzt ist, katalysiert enantioselektive Friedel‐Crafts‐Reaktionen mit hoher Reaktivität und ausgezeichneter Enantioselektivität.