Suraj Kanoo,∥ Eduardo de Pedro Beato,∥ Tim Schulte, Lara Vogelsang, Luca Torkowski, Felix Waldbach, Philipp Hartmann, Riya Kayal, Karl-Josef Dietz, and Tobias Ritter*
J. Am. Chem. Soc. 2025,
https://doi.org/10.1021/jacs.5c11842
Abstract
C–N cross coupling reactions are widely employed for the construction of carbon–nitrogen bonds. However, control of chemoselectivity in the presence of the amino functionality in oligonucleotides remains a challenge. Here, we report the development of a new ruthenium reagent that enables the chemoselective N-arylation of amine–DNA conjugates with distinct chemoselectivity when compared to conventional palladium-based C–N bond-forming catalysts. The ruthenium reagent activates commercially available haloarenes in situ via η6 π-arene coordination for subsequent SNAr with the amine. The method is compatible with various commercially available haloarenes and aliphatic amines, and the reaction proceeds under mild conditions.