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...

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Bibliographic Details
Published in:Angewandte Chemie (International ed.) 2018-12, Vol.57 (52), p.17146-17150
Main Authors: Sutyak, Keith B., Lee, Wes, Zavalij, Peter V., Gutierrez, Osvaldo, Davis, Jeffery T.
Format: Article
Language:English
Subjects:
Catalysis
Covalent bonds
G-quadruplex
Guanosine
ONIOM (QM:MM)
Photochemicals
photochemistry
Quantum mechanics
self-assembly
Stereoselectivity
supramolecular catalysis
templated synthesis
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Summary: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