Azomethine ylides, generated from imines derived Ocynnamyl or O-crotonyl salicylaldeyde and α-amino acids, undergo intramolecular 1,3-dipolar cycloaddition, leading to chromene-[4,3-b]-pyrrolidines. Two reaction conditions are used: a) microwave irradiation (200W) assisted heating (185 ºC) of a neat mixture of reagents, and b) conventional heating (170 ºC) in PEG-400 as solvent. In both cases mixture of two epimers at the α-position of the nitrogenatom in the pyrrolidine nucleus was formed through the less energetic endo-approach (B/C ring fusion). In many cases, the formation of the stereoisomer bearing a transarrangement into the B/C ring fusion in high proportions. A comprehensive computational and kinetic simulation studies are detailed. The analysis of the stability of transient 1,3-dipoles, followed by the assessment of intramolecular pathways and kinetic are carefully performed.