title: Organocatalytic Coupling of CO2with a Propargylic Alcohol: A Comprehensive Mechanistic Study.
abstract: The metal-free coupling of a propargylic alcohol with CO2catalysed by guanidine derivatives was investigated in detail through the combination of online kinetic studies by in situ attenuated-total reflection IR (ATR-IR) spectroscopy and DFT calculations. Bicyclic guanidines, namely 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) are effective catalysts for the conversion of 2-methyl-3-butyn-2-ol to α-methylene cyclic carbonate and oxoalkyl acyclic carbonate under mild reaction conditions. The lower selectivity of TBD in comparison with MTBD towards the formation of α-methylene cyclic carbonate was elucidated from DFT calculations and is related to the bifunctional activity (base/H-bond donor) of TBD decreasing the Gibbs free energy of the reaction path for the formation of the acyclic carbonate.
authors.affiliation: Institut des Sciences Moléculaires (ISM), UMR5255 CNRS, Université de Bordeaux, 351 Cours de la libération, 33405, Talence Cedex, France.|Center for Education and Research on Macromolecules (CERM), Chemistry Department, B6a, University of Liège, allée du 6 août, 4000, Liege, Belgium.
authors.forename: Amélie
authors.initials: A
authors.lastname: Boyaval
authors.affiliation: Institut des Sciences Moléculaires (ISM), UMR5255 CNRS, Université de Bordeaux, 351 Cours de la libération, 33405, Talence Cedex, France.
authors.forename: Raphaël
authors.initials: R
authors.lastname: Méreau
authors.affiliation: Center for Education and Research on Macromolecules (CERM), Chemistry Department, B6a, University of Liège, allée du 6 août, 4000, Liege, Belgium.
authors.forename: Bruno
authors.initials: B
authors.lastname: Grignard
authors.affiliation: Center for Education and Research on Macromolecules (CERM), Chemistry Department, B6a, University of Liège, allée du 6 août, 4000, Liege, Belgium.
authors.forename: Christophe
authors.initials: C
authors.lastname: Detrembleur
authors.affiliation: Center for Education and Research on Macromolecules (CERM), Chemistry Department, B6a, University of Liège, allée du 6 août, 4000, Liege, Belgium.
authors.forename: Christine
authors.initials: C
authors.lastname: Jerome
authors.affiliation: Institut des Sciences Moléculaires (ISM), UMR5255 CNRS, Université de Bordeaux, 351 Cours de la libération, 33405, Talence Cedex, France.
authors.forename: Thierry
authors.initials: T
authors.lastname: Tassaing
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D020005:Propanols / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D000480:Alkynes; D020005:Propanols; D002245:Carbon Dioxide; C028255:propargyl alcohol
keywords: DFT calculations; bicyclic guanidine; carbon dioxide; organocatalysis; α-methylene carbonate