In this work, a library of 63 derivatives of potentially bioactive oximes, oxime ethers, oximes carbamates, and α-acylamino-amides containing an imidazolium and/or quinuclidinium nucleus was prepared. In addition, α-acylamino-amides containing other heterocyclic subunits (pyridine, indole tetrazole and thiophene) were also synthesized in order to obtain the most diverse library of new compounds that have not been described in the literature so far. Classical methods of synthesis in solution, mechanochemical and microwave synthesis were used for the synthesis of compounds. The conditions were varied and the speed and yields of the reactions were compared, as well as the stereochemistry of the products formed in the case of ether oximes. The conditions for the stereospecific synthesis of four quinuclidine oxime ethers were optimized by mechanochemical synthesis without solvent and with sodium hydroxide as a base (anti isomer is formed). Nuclear magnetic resonance spectroscopy was used to determine the ratio of ether oxime isomers and α-acylamino-amide conformers in the solution. The mechanism and stereochemistry of quinuclidin-3-one oxime ether formation and the conformational space of α-acylamino-amide were studied by quantum-chemical calculations.