title: Disassembly kinetics of quinone-methide-based self-immolative spacers that contain aromatic nitrogen heterocycles.
abstract: We prepared several pyridine- and pyrimidine-based self-immolative spacer groups to evaluate the significance of the resonance energy of the spacer aromatic ring on the kinetics of 1,4- and 1,6-elimination reactions, which govern spacer disassembly. Subsequently, we relied on a photoactivation procedure to accurately analyze the disassembly kinetics. Beyond providing new results that are relevant for deriving quantitative structure-property relationships, herein, we demonstrate that pH value can be used as an efficient parameter to finely control the disassembly time of a self-immolative spacer after an initial activation.
authors.affiliation: Institut Curie, Centre de Recherche, 26 rue d'Ulm, Paris F-75248 (France), Fax: (+33) 1-56-24-66-31; CNRS, UMR 176, 26 rue d'Ulm, Paris F-75248 (France); Ecole Normale Supérieure, Département de Chimie, UMR CNRS-ENS-UPMC 8640 PASTEUR, 24 rue Lhomond, 75231 Paris (France).
authors.forename: Ahmed
authors.initials: A
authors.lastname: Alouane
authors.forename: Raphaël
authors.initials: R
authors.lastname: Labruère
authors.forename: Katherine J
authors.initials: KJ
authors.lastname: Silvestre
authors.forename: Thomas
authors.initials: T
authors.lastname: Le Saux
authors.forename: Frédéric
authors.initials: F
authors.lastname: Schmidt
authors.forename: Ludovic
authors.initials: L
authors.lastname: Jullien
mesh_terms: D006571:Heterocyclic Compounds / Q000737:chemistry*; D007700:Kinetics; D015394:Molecular Structure; D017672:Nitrogen Compounds / Q000737:chemistry*; D011809:Quinones / Q000737:chemistry*
chemical_list: D006571:Heterocyclic Compounds; D017672:Nitrogen Compounds; D011809:Quinones
keywords: kinetics; nitrogen heterocycles; photochemistry; pyrimidines; self-immolation