Fast, Regioselective\nAminolysis of Tetrasubstituted\nCyclic Carbonates and Application to Recyclable Thermoplastics and\nThermosets

Herein,\nthe long-standing challenge of the ring-opening aminolysis\nof CO<sub>2</sub>-derived tetrasubstituted cyclic carbonates at room\ntemperature (r.T) is overcome under catalyst-free conditions. Molecular\ndesign of the cyclic carbonate by substitution of an alkyl group by\na thioether unlocks quantitative conversion at r.T and ensures total\nregioselectivity toward highly substituted oxazolidone scaffolds.\nAn in-depth rationalization of the high reactivity of these cyclic\ncarbonate structures and of the aminolysis reaction mechanism is provided\nby a computational study supporting experimental observations. The\nhigh efficiency of the reaction is then translated to the deconstruction\nof high-performance thermoplastics containing tetrasubstituted cyclic\ncarbonate linkages to deliver building blocks that are reused for\ndesigning recyclable thermosets bearing dynamic <i>N</i>,<i>S</i>-acetal linkages.