Templating and Catalyzing [2+2] Photocycloaddition in Solution Using a Dynamic G‐Quadruplex
We describe a templating/covalent capture strategy that enables photochemical formation of 8 cyclobutanes in one noncovalent assembly. This process was characterized by experiment and quantum mechanical/molecular mechanics (ONIOM) calculations. Thus, KI and 16 units of 5′‐cinnamate guanosine form a...
Gespeichert in:
Veröffentlicht in: | Angewandte Chemie (International ed.) 2018-12, Vol.57 (52), p.17146-17150 |
---|---|
Hauptverfasser: | , , , , |
Format: | Artikel |
Sprache: | eng |
Schlagworte: | |
Online-Zugang: | Volltext |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Zusammenfassung: | We describe a templating/covalent capture strategy that enables photochemical formation of 8 cyclobutanes in one noncovalent assembly. This process was characterized by experiment and quantum mechanical/molecular mechanics (ONIOM) calculations. Thus, KI and 16 units of 5′‐cinnamate guanosine form a G‐quadruplex where C=C π bonds in neighboring G4‐quartets are separated by 3.3 Å, enabling [2+2] photocycloaddition in solution. This reaction is high‐yielding (>90 %), regio‐ and diastereoselective. Since all components are in dynamic equilibrium this photocycloaddition is catalytic in K+.
A templating/covalent capture strategy enables photochemical formation of eight cyclobutanes in one noncovalent assembly. KI and 16 units of 5′‐cinnamate guanosine form a G‐quadruplex where C=C bonds in neighboring G4‐quartets are separated by 3.3 Å, enabling [2+2] photocycloaddition in solution. This reaction is high‐yielding (>90 %), regio‐ and diastereoselective. |
---|---|
ISSN: | 1433-7851 1521-3773 |
DOI: | 10.1002/anie.201811202 |