Related Experiment Video
Updated: Jul 31, 2026

Chemoselective Modification of Viral Surfaces via Bioorthogonal Click Chemistry
Published on: August 19, 2012
RNA-tethered phenyl azide photocrosslinking via a short-lived indiscriminant electrophile
Karen L Buchmueller1, Brian T Hill, Matthew S Platz
1Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27599-3290, USA.
Abstract:
Arylazide mediated photocrosslinking has been widely used to obtain structural constraints in biological systems, even though the reactive species generated upon photolysis in aqueous solution have not been well characterized. We establish a mechanistic framework for formation of adducts between photoactivated 3-hydroxyphenyl azide and RNA. Tethered to an internal site in an RNA duplex via a 2'-amido linkage, photolysis of the aryl azide yields a cross-strand cross-link. Analysis of the ability of reagents with diagnostic reactivities to intercept formation of this cross-strand cross-link supports the assignment that the photoactivated intermediate is the ketenimine or a ketenimine-derived ring expansion product. Neither the initially produced singlet nitrene nor the subsequently formed triplet nitrene contribute to cross-link formation. Argon matrix and time-resolved solution experiments show that photolysis of free 3-hydroxyphenyl azide releases (in
More Related Videos
Related Concept Videos
Base-Catalyzed Ring-Opening of Epoxides
Thermal and Photochemical Electrocyclic Reactions: Overview
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Aryldiazonium Salts to Azo Dyes: Diazo Coupling
Olefin Metathesis Polymerization: Acyclic Diene Metathesis (ADMET)
Similar to cross-metathesis, ADMET also involves the formation of metallacyclobutane intermediate by [2+2] cycloaddition of one of the double bonds of a terminal diene with...
Cycloaddition Reactions: MO Requirements for Photochemical Activation

