Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System

Axial chirality is a prevalent and important phenomenon in chemistry. Herein we report a combination of dynamic covalent chemistry and axial chirality for the development of a versatile platform for the binding and chirality sensing of multiple classes of mononucleophiles. An equilibrium between an...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2018-01, Vol.57 (5), p.1300-1305
Main Authors: Ni, Cailing, Zha, Daijun, Ye, Hebo, Hai, Yu, Zhou, Yuntao, Anslyn, Eric V., You, Lei
Format: Article
Language:English
Subjects:
Alcohols
Amines
axial chirality
Biphenyl
Chemical bonds
Chemistry
Chirality
chirality sensing
Circular dichroism
Covalence
Detection
Dichroism
dynamic covalent chemistry
External stimuli
Handedness
Helicity
molecular recognition
Nucleophiles
Scaffolds
Selectivity
self-assembly
Thiols
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Summary:Axial chirality is a prevalent and important phenomenon in chemistry. Herein we report a combination of dynamic covalent chemistry and axial chirality for the development of a versatile platform for the binding and chirality sensing of multiple classes of mononucleophiles. An equilibrium between an open aldehyde and its cyclic hemiaminal within biphenyl derivatives enabled the dynamic incorporation of a broad range of alcohols, thiols, primary amines, and secondary amines with high efficiency. Selectivity toward different classes of nucleophiles was also achieved by regulating the distinct reactivity of the system with external stimuli. Through induced helicity as a result of central‐to‐axial chirality transfer, the handedness and ee values of chiral monoalcohol and monoamine analytes were reported by circular dichroism. The strategies introduced herein should find application in many contexts, including assembly, sensing, and labeling. Talking sense: A convergence of the concepts of dynamic covalent chemistry and axial chirality enabled the reversible incorporation and chirality sensing of multiple classes of mononucleophiles (see picture). Selectivity toward different classes of nucleophiles could also be induced by regulating the distinct reactivity of the system with external stimuli.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201711602