Lewis acid catalyzed coupling reactions between epoxides and different heterocumulenes can lead to a wide variety of interesting heterocycles. Aluminium aminotriphenolates (ATP) have proven to be very active catalyst in the activation of epoxides towards the formation of cyclic carbonates via CO₂ couplings, and we set out to explore further catalytic potential in the synthesis of other heterocyclic targets. Aminotriphenolate complexes are tunable and readily synthesized catalysts with great potential in Lewis acid catalysis. Using this type of Lewis acids (combined with halide cocatalysts), we have developed a series of straightforward and simple methodologies for the synthesis of oxazolidinones, cyclic sulfites, and cyclic carbonates with challenging substitution patterns. We have specially focused on the diastereoselectivity of the products, and have developed means to control it by identifying conditions which favour different intermediates in the reaction pathway. Finally we have investigated how this heterocycles can be useful synthons for the synthesis of other value added compounds.