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Updated: Mar 10, 2026

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
Published on: November 9, 2019
Organocatalytic Coupling of CO2 with a Propargylic Alcohol: A Comprehensive Mechanistic Study
Amélie Boyaval1,2, Raphaël Méreau1, Bruno Grignard2
1Institut des Sciences Moléculaires (ISM), UMR5255 CNRS, Université de Bordeaux, 351 Cours de la libération, 33405, Talence Cedex, France.
Abstract:
The metal-free coupling of a propargylic alcohol with CO2 catalysed 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.
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