Volume 25, Issue 47 p. 11074-11079
Full Paper

Delineation of the Critical Parameters of Salt Catalysts in the N-Formylation of Amines with CO2

Martin Hulla

Martin Hulla

Institute of Chemistry and Chemical Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

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Dr. Daniel Ortiz

Dr. Daniel Ortiz

Institute of Chemistry and Chemical Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

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Dr. Sergey Katsyuba

Dr. Sergey Katsyuba

Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center of RAS, Arbuzov st. 8, 420088 Kazan, Russia

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Dmitry Vasilyev

Dmitry Vasilyev

Institute of Chemistry and Chemical Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

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Prof. Dr. Paul J. Dyson

Corresponding Author

Prof. Dr. Paul J. Dyson

Institute of Chemistry and Chemical Engineering, École Polytechnique Fédérale de Lausanne (EPFL), 1015 Lausanne, Switzerland

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First published: 21 May 2019
Citations: 25

Graphical Abstract

Unbound and basic: Almost all salts promote the N-formylation of amines with CO2. However, not all do it well. Herein, we present the physical parameters of salt catalysts critical for high activity. Namely their basicity, which is linearly proportionate to the catalytic activity of the salt and the extent of ion pairing, which also impacts significantly on the activity.

Abstract

N-formylation of amines combining CO2 as a C1 source with a hydrosilane reducing agent is a convenient route for the synthesis of N-formylated compounds. A large number of salts including ionic liquids (ILs) have been shown to efficiently catalyze the reaction and, yet, the key features of the catalyst remain unclear and the best salt catalysts for the reaction remain unknown. Here we demonstrate the detrimental effect of ion pairing on the catalytic activity and illustrate ways in which the strength of the interaction between the ions can be reduced to enhance interactions and, hence, reactivity with the substrates. In contrast to the current hypothesis, we also show that salt catalysts are more active as bases rather than nucleophiles and identify the pKa where the nucleophilic role of the catalyst switches to the more active basic role. The identification of these critical parameters allows the optimum salt catalyst and conditions for an N-formylation reaction to be predicted.

Conflict of interest

The authors declare no conflict of interest.