Engineered non-covalent pi interactions as key elements for chiral recognition

Jin, Ming Yu1,2; Zhen, Qianqian1,2; Xiao, Dengmengfei1,2; Tao, Guanyu1,2; Xing, Xiangyou1,2; Yu, Peiyuan1,2; Xu, Chen1,2

2022-06-07

10.1038/s41467-022-31026-8

NATURE COMMUNICATIONS   Impact Factor & Quartile

2041-1723

["Molecular recognition and self-assembly are often mediated by intermolecular forces involving aromatic pi-systems. Despite the ubiquity of such interactions in biological systems and in the design of functional materials, the elusive nature of aromatic pi interaction results in that they have been seldom used as a design element for promoting challenging chemical reactions. Described here is a well-engineered catalytic system into which non-covalent pi interactions are directly incorporated. Enabled by a lone pair-pi interaction and a pi-pi stacking interaction operating collectively, efficient chiral recognition is successfully achieved in the long-pursued dihydroxylation-based kinetic resolution. Density functional theory calculations shed light on the crucial role played by the lone pair-pi interaction between the carbonyl oxygen of the cinchona alkaloid ligand and the electron-deficient phthalazine pi moiety of the substrate in the stereoselectivity-determining transition states. This discovery serves as a proof-of-principle example showing how the weak non-covalent pi interactions, if ingeniously designed, could be a powerful guide in attaining highly enantioselective catalysis.","Non-covalent pi interactions have been rarely used as a design element for promoting chemical reactions. Here the authors report a Sharpless asymmetric dihydroxylation (SAD)-based kinetic resolution in which a-priori-designed non-covalent forces play a central role in differentiating the enantiomeric substrates."]

SCI

English

NI Journal Papers

First ; Corresponding

Shenzhen Nobel Prize Scientists Laboratory Project[C17783101] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; National Natural Science Foundation of China[K21211026] ; Shenzhen Science and Technology Program["KQTD20180411143514543","K20215006"]

Science & Technology - Other Topics

Multidisciplinary Sciences

WOS:000808128800045

NATURE PORTFOLIO

2-s2.0-85131480154

Web of Science

1.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Shenzhen Grubbs Inst, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Peoples R China

Jin, Ming Yu,Zhen, Qianqian,Xiao, Dengmengfei,et al. Engineered non-covalent pi interactions as key elements for chiral recognition[J]. NATURE COMMUNICATIONS,2022,13(1).

Jin, Ming Yu.,Zhen, Qianqian.,Xiao, Dengmengfei.,Tao, Guanyu.,Xing, Xiangyou.,...&Xu, Chen.(2022).Engineered non-covalent pi interactions as key elements for chiral recognition.NATURE COMMUNICATIONS,13(1).

Jin, Ming Yu,et al."Engineered non-covalent pi interactions as key elements for chiral recognition".NATURE COMMUNICATIONS 13.1(2022).