Unlocking the Potential of Substrate-Directed CO2Activation and Conversion: Pushing the Boundaries of Catalytic Cyclic Carbonate and Carbamate Formation

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/CO(2)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 CO(2)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.