American Chemical Society
ao9b01273_si_001.pdf (7.19 MB)

Regulation of Axial Chirality through Dynamic Covalent Bond Constrained Biaryls

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journal contribution
posted on 2019-06-13, 08:15 authored by Hao Zheng, Cailing Ni, Hang Chen, Daijun Zha, Yu Hai, Hebo Ye, Lei You
A strategy of dynamic covalent chemistry within constrained biaryls was developed for the modulation of axial chirality. The ring fusion partners of amide and aldehyde allowed the manipulation of ring/chain equilibrium and chirality transfer within cyclic diastereomeric hemiaminal. Dynamic covalent reactions (DCRs) with alcohols, thiols, and secondary amines further enabled the reversal of chirality relay and thereby regulation of axial chirality. Moreover, a combination of NMR, X-ray, and density functional theory results shed light on the structural basis of chirality transfer, exhibiting modest to excellent diastereoselectivity under thermodynamic control. The critical role of the amide unit in the modulation of axial chirality was also corroborated. Finally, the chiroptical signal was controlled through changing solvents, DCRs, and stimuli-responsive switching of DCRs.