title: Glycidol: an Hydroxyl-Containing Epoxide Playing the Double Role of Substrate and Catalyst for CO2Cycloaddition Reactions.
abstract: Glycidol is converted into glycerol carbonate (GC) by coupling with CO2in the presence of tetrabutylammonium bromide (TBAB) under mild reaction conditions (T=60 °C, PCO2 =1 MPa) in excellent yields (99 %) and short reaction time (t=3 h). The unusual reactivity of this substrate compared to other epoxides, such as propylene oxide, under the same reaction conditions is clearly related to the presence of a hydroxyl functionality on the oxirane ring. Density functional theory calculations (DFT) supported by1H NMR experiments reveal that the unique behavior of this substrate is a result of the formation of intermolecular hydrogen bonds into a dimeric structure, activating this molecule to nucleophilic attack, and allowing the formation of GC. Furthermore, the glycidol/TBAB catalytic system acts as an efficient organocatalyst for the cycloaddition of CO2to various oxiranes.
authors.affiliation: Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università degli Studi di Salerno, via Giovanni Paolo II, 84084, Fisciano, SA, Italy.|Interuniversity Consortium Chemical Reactivity and Catalysis (CIRCC), via Celso Ulpiani 27, 70126, BA, Italy.
authors.forename: Francesco
authors.identifier: http://orcid.org/0000-0001-6530-7351
authors.initials: F
authors.lastname: Della Monica
authors.affiliation: Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università degli Studi di Salerno, via Giovanni Paolo II, 84084, Fisciano, SA, Italy.|Interuniversity Consortium Chemical Reactivity and Catalysis (CIRCC), via Celso Ulpiani 27, 70126, BA, Italy.
authors.forename: Antonio
authors.initials: A
authors.lastname: Buonerba
authors.affiliation: Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università degli Studi di Salerno, via Giovanni Paolo II, 84084, Fisciano, SA, Italy.|Interuniversity Consortium Chemical Reactivity and Catalysis (CIRCC), via Celso Ulpiani 27, 70126, BA, Italy.
authors.forename: Alfonso
authors.initials: A
authors.lastname: Grassi
authors.affiliation: Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università degli Studi di Salerno, via Giovanni Paolo II, 84084, Fisciano, SA, Italy.|Interuniversity Consortium Chemical Reactivity and Catalysis (CIRCC), via Celso Ulpiani 27, 70126, BA, Italy.
authors.forename: Carmine
authors.identifier: http://orcid.org/0000-0001-7254-8620
authors.initials: C
authors.lastname: Capacchione
authors.affiliation: Dipartimento di Chimica e Biologia "Adolfo Zambelli", Università degli Studi di Salerno, via Giovanni Paolo II, 84084, Fisciano, SA, Italy.|Interuniversity Consortium Chemical Reactivity and Catalysis (CIRCC), via Celso Ulpiani 27, 70126, BA, Italy.
authors.forename: Stefano
authors.initials: S
authors.lastname: Milione
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D061565:Cycloaddition Reaction; D004852:Epoxy Compounds / Q000737:chemistry*; D006860:Hydrogen Bonding; D017665:Hydroxyl Radical / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D020005:Propanols / Q000737:chemistry*
chemical_list: D004852:Epoxy Compounds; D020005:Propanols; D002245:Carbon Dioxide; D017665:Hydroxyl Radical; C004312:glycidol
keywords: carbon dioxide; cycloaddition; density functional theory; epoxide; hydrogen bond