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Tetrabutylammonium Salts: Cheap Catalysts for the Facile and Selective Synthesis of α‐Alkylidene Cyclic Carbonates from Carbon Dioxide and Alkynols
Author(s) -
Méreau Raphaël,
Grignard Bruno,
Boyaval Amélie,
Detrembleur Christophe,
Jerome Christine,
Tassaing Thierry
Publication year - 2018
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201701567
Subject(s) - catalysis , chemistry , selectivity , solvation , solvent , dimethyl carbonate , carbon dioxide , kinetics , inorganic chemistry , methylene , heterogeneous catalysis , organic chemistry , photochemistry , physics , quantum mechanics
n ‐Tetrabutylammonium organic salts were used for the first time as catalysts for the coupling of CO 2 with 2‐methyl‐3‐butyn‐2‐ol to form an α‐methylene cyclic carbonate. Final yields up to 98 % were reached in less than 10 h at 353 K and 3 MPa under solvent‐free conditions. A particular synergistic effect between the cation and the anion of the organocatalyst was demonstrated through catalyst screening. Online kinetic studies by Attenuated Total Reflectance (ATR) IR spectroscopy correlated to DFT calculations revealed compelling evolution of solvation of the catalyst during the reaction that provided insight into the underlying reason for the observed unique kinetics and selectivity. Such in‐depth fundamental mechanistic and kinetic studies enabled determination and comprehension of the key parameters favoring the design of novel, highly active and selective catalysts for valorization of CO 2 as a chemical feedstock.