Selective Catalytic Synthesis of 1,2‐ and 8,9‐Cyclic Limonene Carbonates as Versatile Building Blocks for Novel Hydroxyurethanes

The selective catalytic synthesis of limonene‐derived monofunctional cyclic carbonates and their subsequent functionalisation via thiol–ene addition and amine ring‐opening is reported. A phosphotungstate polyoxometalate catalyst used for limonene epoxidation in the 1,2‐position is shown to also be active in cyclic carbonate synthesis, allowing a two‐step, one‐pot synthesis without intermittent epoxide isolation. When used in conjunction with a classical halide catalyst, the polyoxometalate increased the rate of carbonation in a synergistic double‐activation of both substrates. The cis isomer is shown to be responsible for incomplete conversion and by‐product formation in commercial mixtures of 1,2‐limomene oxide. Carbonation of 8,9‐limonene epoxide furnished the 8,9‐limonene carbonate for the first time. Both cyclic carbonates underwent thiol–ene addition reactions to yield linked di‐monocarbonates, which can be used in linear non‐isocyanate polyurethanes synthesis, as shown by their facile ring‐opening with N‐hexylamine. Thus, the selective catalytic route to monofunctional limonene carbonates gives straightforward access to monomers for novel bio‐based polymers.