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Synthesis of Information-bearing Peptoids and their Sequence-directed Dynamic Covalent Self-assembly
Published on: February 6, 2020
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Versatile Dynamic Covalent Assemblies for Probing π-Stacking and Chirality Induction from Homotopic Faces.
Hebo Ye1, Yu Hai1,2, Yulong Ren1
1State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, 350002, P.R. China.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|January 3, 2017
Summary
This study introduces dynamic covalent reactions for π-stacking systems, enabling quantification of substituent effects. This method also facilitates chirality transfer, offering new avenues for studying weak interactions.
Area of Science:
- Supramolecular Chemistry
- Organic Chemistry
Background:
- Quantifying substituent effects in π-stacking interactions remains challenging.
- Dynamic covalent chemistry offers a versatile platform for molecular assembly.
Purpose of the Study:
- To develop a novel method for building and quantifying π-stacking model systems using dynamic covalent reactions (DCRs).
- To investigate the substituent effects (SEs) in π-stacking interactions.
- To explore the potential for chirality transfer within these DCR-assembled systems.
Main Methods:
- Discovery of a general DCR between 10-methylacridinium ion and primary amines.
- In situ quantification of SEs using competing π-stacking systems via amine exchange.
- Analysis of substituent effects using Hammett plots.
- Chirality transfer studies using α-chiral amines.
Main Results:
- A general DCR was established, where π-stacking stabilizes the adduct.
- SEs were quantified and shown to be dominated by electrostatic contributions, correlating linearly with σm.
- The additivity of SEs supports a direct interaction model.
- Chirality transfer from α-chiral amines to homotopic faces was achieved via π-stacking.
Conclusions:
- Dynamic covalent assembly provides a powerful strategy for probing weak interactions like π-stacking.
- This approach allows for facile quantification of SEs and demonstrates control over chirality transfer.
- The methodology holds promise for future research in supramolecular chemistry and chiral manipulation.
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