Templating and Catalyzing [2+2] Photocycloaddition in Solution Using a Dynamic G‐Quadruplex. (25th November 2018)

• Record Type: Journal Article
• Authors: Sutyak, Keith B.; Lee, Wes; Zavalij, Peter V.; Gutierrez, Osvaldo; Davis, Jeffery T.
• Is Part Of: Angewandte Chemie. Volume 130:Number 52(2018)
• Page Start: 17392
• Page End: 17396
• Publication Date: 2018-11-25
• Subjects: G-Quadruplexe -- Photochemie -- Selbstorganisation -- Supramolekulare Katalyse -- Templatsynthesen; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201811202
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: 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 + . Abstract : Templatsynthese und kovalenter Einfang ermöglichen die photochemische Bildung von acht Cyclobutanen in einem einzelnen nichtkovalenten Aggregat. KI und 16 Einheiten 5′‐Cinnamatguanosin bilden einen G‐Quadruplex, in dem C=C‐Bindungen in benachbarten G4‐Quartetts 3.3 Å voneinander entfernt sind, sodass eine [2+2]‐Photocycloaddition in Lösung ablaufen kann. Diese Reaktion ist hoch effizient (>90 % Ausbeute), regio‐ und diastereoselektiv.