The regioselective synthesis of carbamates from bio-derived cyclic carbonates and amines by using 1,5,7-triazabicyclo[4.4.0]dec-5-ene as an organocatalyst is reported. This methodology led to the preparation of a wide range of bio-sourced hydroxyurethanes from furan-, carvone- and limonene-based scaffolds under solvent-free and mild reaction conditions. Moreover, a comprehensive analysis of the process allowed us to optimize the catalyst loading with little or no impact on the process regioselectivity.

The regioselective synthesis of carbamates from bio-derived cyclic carbonates and amines by using 1,5,7-triazabicyclo[4.4.0]dec-5-ene as an organocatalyst is reported. This methodology led to the preparation of a wide range of bio-sourced hydroxyurethanes from furan-, carvone- and limonene-based scaffolds under solvent-free and mild reaction conditions. Moreover, a comprehensive analysis of the process allowed us to optimize the catalyst loading with little or no impact on the process regioselectivity.

The reaction between bis(1,2,3-triazol-1-yl)methane derivatives and nBuLi and various aldehydes, yielded novel neutral ligand precursors incorporating alcohol functional groups. The resulting compounds exhibited distinct characteristics depending on the steric hindrance of the aldehyde employed. In instances where aromatic aldehydes were utilized, functionalization occurred at the methine group bridging both triazole rings. Conversely, the use of pivalic aldehyde prompted functionalization at the C5 position of the triazole ring. These compounds were subsequently employed as ligand precursors in the synthesis of organometallic aluminum and zinc complexes, yielding dinuclear complexes with high efficiency. The structural elucidation of all compounds was accomplished through spectroscopic methods and validated by X-ray crystallography. Preliminary catalytic investigations into the coupling reaction of cyclohexene oxide and CO2 revealed that aluminum and zinc complexes catalyzed the selective formation of polyether and polycarbonate materials, respectively.

The reaction between bis(1,2,3-triazol-1-yl)methane derivatives and nBuLi and various aldehydes, yielded novel neutral ligand precursors incorporating alcohol functional groups. The resulting compounds exhibited distinct characteristics depending on the steric hindrance of the aldehyde employed. In instances where aromatic aldehydes were utilized, functionalization occurred at the methine group bridging both triazole rings. Conversely, the use of pivalic aldehyde prompted functionalization at the C5 position of the triazole ring. These compounds were subsequently employed as ligand precursors in the synthesis of organometallic aluminum and zinc complexes, yielding dinuclear complexes with high efficiency. The structural elucidation of all compounds was accomplished through spectroscopic methods and validated by X-ray crystallography. Preliminary catalytic investigations into the coupling reaction of cyclohexene oxide and CO2 revealed that aluminum and zinc complexes catalyzed the selective formation of polyether and polycarbonate materials, respectively.

The coupling reaction of carbon dioxide and highly-substituted epoxides derived from renewable resources such as fatty acids and waste vegetable oils (cooking oils derived from olive and sunflower) leads to the synthesis of new bio-derived cyclic carbonates using efficient metal-free bifunctional organocatalysts under mild and solvent-free reaction conditions. Once cyclic carbonates derived from biobased sources were synthesized, the design of non-isocyanate polyurethanes (NIPUs) with different chemical structures was investigated by their reaction with a broad substrate scope of diamines. The NIPUs materials were characterized by spectroscopic techniques (NMR and IR) and their molecular weights and polydispersities were determined by GPC studies. Finally, thermal properties of the polymers were studied by DSC and TGA analyses.

The coupling reaction of carbon dioxide and highly-substituted epoxides derived from renewable resources such as fatty acids and waste vegetable oils (cooking oils derived from olive and sunflower) leads to the synthesis of new bio-derived cyclic carbonates using efficient metal-free bifunctional organocatalysts under mild and solvent-free reaction conditions. Once cyclic carbonates derived from biobased sources were synthesized, the design of non-isocyanate polyurethanes (NIPUs) with different chemical structures was investigated by their reaction with a broad substrate scope of diamines. The NIPUs materials were characterized by spectroscopic techniques (NMR and IR) and their molecular weights and polydispersities were determined by GPC studies. Finally, thermal properties of the polymers were studied by DSC and TGA analyses.