The reactions of dimethyl carbonate and its derivatives

The worldwide urge to embrace a sustainable and bio-compatible chemistry has led industry and academia\udto develop of chlorine-free methodologies focused on the use of CO2 and CO2-based compounds\udas feedstocks, promoters and reaction media. In this scenario, dialkyl carbonates (DACs) and in particular\uddimethyl carbonate (DMC) occupy a privileged position due to their low toxicity, high biodegradability and\udpeculiar reactivity. Nowadays, the large-scale production of DACs is carried out through clean processes\ud(i.e., phosgene-free processes), which include the direct insertion of CO2 into epoxides, allowing – in\udprinciple – recycling of the carbon dioxide emitted during carbonate degradation. This groundbreaking\udachievement has definitely drawn attention toward the conception of procedures to activate the rather\udstable DACs with the aim of employing these compounds as green alternatives to their reactive chlorinated\udanalogues. DACs are ambident electrophiles, which under appropriate conditions can undergo\udBAc2- or BAl2-nucleophilic substitution to give, respectively, alkoxycarbonylation and alkylation reactions.\udThe many efforts devoted to improving the industrial suitability of organic carbonates have unveiled an\udintriguing and innovative chemistry as demonstrated by the numerous publications and patents published\udon these compounds over the last thirty years. This review reports on DACs as alkoxycarbonylating agents\udand their applications in industry and fine synthesis, as well as alkylating agents including allylic alkylation\udusing palladium catalysts and the Pd/Ti bimetallic system and anchimerically driven alkylations via mustard\udcarbonates. Moreover, the reactivity of organic carbonates toward several substrates and under different\udreaction conditions is described along with some distinctive DAC-mediated cyclization and transposition\udreactions. The synthesis of olefins and ethers under both liquid and gas phase conditions via thermal decarboxylation\udof organic carbonates is also reported