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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
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201811202
Subject(s) - oniom , cyclobutanes , g quadruplex , chemistry , covalent bond , guanosine , non covalent interactions , supramolecular catalysis , dynamic covalent chemistry , catalysis , quantum chemical , computational chemistry , supramolecular chemistry , stereochemistry , cycloaddition , crystallography , organic chemistry , molecule , hydrogen bond , dna , crystal structure , biochemistry
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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