Interplay of chloride levels and palladium(ii)-catalyzed O -deallenylation bioorthogonal uncaging reactions.

Autor: Dal Forno GM; Laboratory of Biomimetic Catalysis (LaCBio), Department of Chemistry, Federal University of Santa Catarina (UFSC) Campus Trindade Florianópolis 88040-900 SC Brazil josiel.domingos@ufsc.br., Latocheski E; Laboratory of Biomimetic Catalysis (LaCBio), Department of Chemistry, Federal University of Santa Catarina (UFSC) Campus Trindade Florianópolis 88040-900 SC Brazil josiel.domingos@ufsc.br., Navo CD; Center for Cooperative Research in Biosciences (CIC BioGUNE), Basque Research and Technology Alliance (BRTA) Bizkaia Technology Park, Building 800, Derio 48160 Spain., Albuquerque BL; Laboratory of Biomimetic Catalysis (LaCBio), Department of Chemistry, Federal University of Santa Catarina (UFSC) Campus Trindade Florianópolis 88040-900 SC Brazil josiel.domingos@ufsc.br., St John AL; Laboratory of Biomimetic Catalysis (LaCBio), Department of Chemistry, Federal University of Santa Catarina (UFSC) Campus Trindade Florianópolis 88040-900 SC Brazil josiel.domingos@ufsc.br., Avenier F; Institut de Chimie Moléculaire et des Matériaux d'Orsay (UMR 8182), Université Paris Saclay 9140 Orsay Cedex France., Jiménez-Osés G; Center for Cooperative Research in Biosciences (CIC BioGUNE), Basque Research and Technology Alliance (BRTA) Bizkaia Technology Park, Building 800, Derio 48160 Spain.; Ikerbasque, Basque Foundation for Science 48013 Bilbao Spain., Domingos JB; Laboratory of Biomimetic Catalysis (LaCBio), Department of Chemistry, Federal University of Santa Catarina (UFSC) Campus Trindade Florianópolis 88040-900 SC Brazil josiel.domingos@ufsc.br.
Jazyk: angličtina
Zdroj: Chemical science [Chem Sci] 2024 Feb 16; Vol. 15 (12), pp. 4458-4465. Date of Electronic Publication: 2024 Feb 16 (Print Publication: 2024).
DOI: 10.1039/d3sc06408e
Abstrakt: The palladium-mediated uncaging reaction of allene substrates remains a promising yet often overlooked strategy in the realm of bioorthogonal chemistry. This method exhibits high kinetic rates, rivaling those of the widely employed allylic and propargylic protecting groups. In this study, we investigate into the mechanistic aspects of the C-O bond-cleavage deallenylation reaction, examining how chloride levels influence the kinetics when triggered by Pd(ii) complexes. Focusing on the deallenylation of 1,2-allenyl protected 4-methylumbelliferone promoted by Allyl 2 Pd 2 Cl 2 , our findings reveal that reaction rates are higher in environments with lower chloride concentrations, mirroring intracellular conditions, compared to elevated chloride concentrations typical of extracellular conditions. Through kinetic and spectroscopic experiments, combined with DFT calculations, we uncover a detailed mechanism that identifies AllylPd(H 2 O) 2 as the predominant active species. These insights provide the basis for the design of π-allylpalladium catalysts suited for selective uncaging within specific cellular environments, potentially enhancing targeted therapeutic applications.
Competing Interests: The authors declare no competing interests.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
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