Disassembly Kinetics of Quinone‐Methide‐Based Self‐Immolative Spacers that Contain Aromatic Nitrogen Heterocycles |
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| Authors: | Ahmed Alouane Dr Raphaël Labruère Katherine J Silvestre Dr Thomas Le?Saux Dr Frédéric Schmidt Prof?Dr Ludovic Jullien |
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| Institution: | 1. Institut Curie, Centre de Recherche, 26 rue d'Ulm, Paris F‐75248 (France), Fax: (+33)?1‐56‐24‐66‐31;2. CNRS, UMR 176, 26 rue d'Ulm, Paris F‐75248 (France);3. Ecole Normale Supérieure, Département de Chimie, UMR CNRS‐ENS‐UPMC 8640 PASTEUR, 24 rue Lhomond, 75231 Paris (France);4. Current address: Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR CNRS 8182, Université Paris Sud, Orsay, 91405 Cedex (France);5. UPMC Univ. Paris 6, 4 Place Jussieu, 75232 Paris (France) |
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| 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. |
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| Keywords: | kinetics nitrogen heterocycles photochemistry pyrimidines self‐immolation |
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