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Templating and Catalyzing [2+2] Photocycloaddition in Solution Using a Dynamic G‐Quadruplex
Author(s) -
Sutyak Keith B.,
Lee Wes,
Zavalij Peter V.,
Gutierrez Osvaldo,
Davis Jeffery T.
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201811202
Subject(s) - oniom , cyclobutanes , g quadruplex , covalent bond , chemistry , guanosine , catalysis , non covalent interactions , supramolecular catalysis , quantum chemical , tetrad , computational chemistry , stereochemistry , supramolecular chemistry , crystallography , cycloaddition , organic chemistry , molecule , hydrogen bond , physics , crystal structure , dna , biochemistry , mathematical physics
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 G 4 ‐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 + .
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