Glycidol: an Hydroxyl-Containing Epoxide Playing the Double Role of Substrate and Catalyst for CO2 Cycloaddition Reactions

作者：Della Monica Francesco; Buonerba Antonio; Grassi Alfonso; Capacchione Carmine^*; Milione Stefano

来源：Chemsuschem, 2016, 9(24): 3457-3464.

DOI：10.1002/cssc.201601154

• carbon dioxide
• cycloaddition
• density functional theory
• epoxide
• hydrogen bond

Glycidol is converted into glycerol carbonate (GC) by coupling with CO2 in the presence of tetrabutylammonium bromide (TBAB) under mild reaction conditions (T = 60 degrees C, P-CO2 = 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 by H-1 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 CO2 to various oxiranes.

• 出版日期2016-12-20