Distorted aryl homochirality controlled byβ-sheet folding

查看全文 作　　者：Yunying [1]Xu;Aiyou [1]Hao;Pengyao [1]Xing 机构地区：[1]School of Chemistry and Chemical Engineering,Shandong University,Ji’nan 250100,China 出　　处：《Chinese Chemical Letters》索引2023年第34卷第11期,共6页 基　　金：supported by the National Natural Science Foundation of China(Nos.21901145,22171165);the financial support from Youth cross-scientific innovation group of Shandong University(No.2020QNQT003). 摘　　要：Distortion of planar aromatics occurs in the fused rings conjugated with bulky substituents,which generates racemic enantiomers with high transformation energy barriers.However,direct synthesis of homochiral distorted aryl compounds is a very challenging task.Here,we presented a molecular folding strategy to control distorted aryl homochirality.Amino acids and their derivatives conjugated on the polycyclic aromatic hydrocarbons including benzenes,naphthalenes and triphenylenes,which formed parallelβ-sheet arrays through intramolecular hydrogen bonds.The folding behavior enabled distorted or twisted geometry of aromatics,of which the handedness was associated with the absolute chirality of amino acids.X-ray crystallography,theoretical calculations and circular dichroism spectroscopy verified the distorted homochirality in the solid and solution phase.The relatively small rotational barrier between the enantiomers made the molecule sensitive to the environment and thus realized the solvent-controlled chiral inversion.Theβ-sheet folding strategy can be widely used in polycyclic aromatic hydrocarbons with various functions,which provided a promising strategy to control inherent chirality of aromatics with adaptive chiroptical responses. 关 键 词：Distorted chirality FOLDING Solvent strategy Chiroptical activity