title: CuAAC Click Reactions in the Gas Phase: Unveiling the Reactivity of Bis-Copper Intermediates.
abstract: Copper-catalysed azide alkyne cycloaddition (CuAAC) has been considered a breakthrough transformation over the last 15 years. Its debated mechanism arouses continuously growing interest. By means of a mass spectrometer modified ad hoc, the entire catalytic cycle of CuAAC reaction has been investigated in the gas phase. Ion-molecule reactions were performed inside the mass spectrometer to reproduce step-by-step, at a molecular level, the complete catalytic cycle of the click reaction. We successfully challenged the reactivity of elusive mono- and bis-copper intermediates by ion-molecule reactions leading to the production of mass-characterized triazole products, paving the way for detailed energetic studies to be performed in the gas phase. The structures of the relevant species, calculated at a DFT level, helped rationalise our experimental results.
authors: UMR CNRS 6521, CEMCA, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, CS 93837, 29238, Cedex 3, France.
authors: Claudio
authors: C
authors: Iacobucci
authors: UMR CNRS 6521, CEMCA, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, CS 93837, 29238, Cedex 3, France.
authors: Alexandre
authors: A
authors: Lebon
authors: Department Physical and Chemical Sciences, University of L'Aquila, Via Vetoio, 67100, L'Aquila, Italy.
authors: Francesco
authors: F
authors: De Angelis
authors: UMR CNRS 6521, CEMCA, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, CS 93837, 29238, Cedex 3, France.
authors: Antony
authors: A
authors: Memboeuf
keywords: click chemistry; copper; cycloaddition; gas-phase reactions