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CYCLIC CARBAMATE FORMATION THROUGH PALLADIUM- CATALYSED CO2 ABSORPTION BY PROPARGYLIC AMINES

The rise of atmospheric CO2 presents the biggest long-term challenge for the global climate and great efforts are being made to develop efficient and cost-effective CO2 capture and storage technologies. In organic synthesis, this has led to an increased interest in using CO2 as a cheap and readily available C1 synthon. Building on previously published work in this area, 1 we have synthesized several propargylic amine substrates and tested their ability to form carbamates through CO2 absorption. The carbamate forming reaction was coupled to C-C bond formation using a palladium catalyst and several allyl-, aryl- and vinyl- substrates. The thermodynamics of the CO2-absorbing reactions have been modelled using the Gaussian 16 software to find the most favorable substrates. We have optimized the reaction conditions to produce allylated carbamates in intermediate yields, finding that copper (I) co-catalysts can significantly improve the reaction yield. We have also synthesized several substrates for an intramolecular version of this reaction which will be explored at a later date. The mechanism of this reaction has also been modelled in silico, with preliminary NMR studies indicating that an unstable intermediate is formed by a reaction between the propargylic alcohol and a palladium(II) catalyst.

CO2 capturing, carbamate formation, Pd

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