Volume 13, Issue 23 p. 6056-6065
Concept

Unlocking the Potential of Substrate-Directed CO2 Activation and Conversion: Pushing the Boundaries of Catalytic Cyclic Carbonate and Carbamate Formation

Dr. Bart Limburg

Dr. Bart Limburg

Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain

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Àlex Cristòfol

Àlex Cristòfol

Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain

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Dr. Francesco Della Monica

Dr. Francesco Della Monica

Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain

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Prof. Arjan W. Kleij

Corresponding Author

Prof. Arjan W. Kleij

Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain

Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010 Barcelona, Spain

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First published: 06 October 2020
Citations: 34

Graphical Abstract

Who's in control? Substrate-assisted nonreductive carbon dioxide conversion is a recently emerged concept that has significantly pushed the existing boundaries of catalytic formation of CO2-based heterocycles. The key mechanistic principles together with the new synthetic opportunities that have arisen from this approach are delineated, and areas with new potential and future developments are identified.

Abstract

The unparalleled potential of substrate-induced reactivity modes in the catalytic conversion of carbon dioxide and alcohol or amine functionalized epoxides is discussed in relation to more conventional epoxide/CO2 coupling strategies. This conceptually new approach allows for a substantial extension of the substitution degree and functionality of cyclic carbonate/carbamate products, which are predominant products in the area of nonreductive CO2 transformations. Apart from the creation of an advanced library of CO2-based heterocyclic products and intermediates, also the underlying mechanistic reasons for this novel reactivity profile are debated with a prominent role for the design and structure of the involved catalysts.

Conflict of interest

The authors declare no conflict of interest.