Pivotal Role of the Basic Character of Organic and Salt Catalysts in C-N Bond Forming Reactions of Amines with CO2

Angewandte Chemie
Martin Hulla, Paul J Dyson

Abstract

Organocatalysts promote a range of C-N bond forming reactions of amines with CO2 . Herein, we review these reactions and attempt to identify the unifying features of the catalysts that allows them to promote a multitude of seemingly unrelated reactions. Analysis of the literature shows that these reactions predominantly proceed by carbamate salt formation in the form [BaseH][RR'NCOO]. The anion of the carbamate salt acts as a nucleophile in hydrosilane reductions of CO2 , internal cyclization reactions or after dehydration as an electrophile in the synthesis of urea derivatives. The reactions are enhanced by polar aprotic solvents and can be either promoted or hindered by H-bonding interactions. The predominant role of all types of organic and salt catalysts (including ionic liquids, ILs) is the stabilization of the carbamate salt, mostly by acting as a base. Catalytic enhancement depends on the combination of the amine, the base strength, the solvent, steric factors, ion pairing and H-bonding. A linear relationship between the base strength and the reaction yield has been demonstrated with IL catalysts in the synthesis of formamides and quinazoline-2,4-diones. The role of organocatalysts in the reactions indicates that all bas...Continue Reading

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Citations

Aug 14, 2020·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Giulio BrescianiFabio Marchetti
Oct 20, 2020·Chemical Communications : Chem Comm·Soumi ChakrabortySwadhin K Mandal
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Jun 8, 2021·Chemical Science·Sreejyothi P, Swadhin K Mandal
May 23, 2021·Chemistry : a European Journal·P SreejyothiSwadhin K Mandal
Jul 25, 2021·Chemical Communications : Chem Comm·Kazuto TakaishiTadashi Ema

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