A versatile, facile and concise approach to access to highly substituted functionalized 2-(pyrrolidin-1-yl)thiazole ring system is accomplished. The efficient protocol proceeds by the reaction of corresponding racemic or enantiomerically enriched pyrrolidines and readily available benzoylisothiocyanate in acetonitrile followed by sequential reaction of readily available alpha-bromo ketones in acetone. The selectivity and good yield in the desired product is another important advantage of this reaction protocol. In a few cases, the resulting Nbenzoylthiourea intermediate cyclizes spontaneously before reacting with the benzophenone component. Finally, a wide study of the biological scope of this new bisheterocyclic molecules is reported.

The enantioselective formation of nitroprolinates followed by diastereoselective Michael‐type addition onto a second unit of the nitro alkene is studied. The reaction occurred in a one pot‐sequential process controlled by the chiral phosphoramidite⋅silver benzoate complex. The origin of the high diastereoselectivity is studied by DFT computational analysis where the crucial effect of the benzoic acid is justified. The employment of this strategy to the preparation of pyrazine‐2‐ones is also surveyed, as well as the preparation of diketopiperazines from enantiomerically enriched exo‐prolinates using conventional N‐acylation‐amination‐cyclization steps.

The enantioselective 1,3-dipolar cycloaddition between imino esters and (Z)-nitroalkenes bearing a masked amino group in the β-position was studied using several chiral ligands and silver salts. The optimized reaction conditions were directly applied to the study of the scope of the reaction. The determination of the absolute configuration was evaluated using NMR experiments and electronic circular dichroism (ECD). The reduction and hydrolysis of both groups was performed to generate in an excellent enantiomeric ratio the corresponding cis-2,3-diaminoprolinate.