A novel three‐step four‐transformation approach to highly functionalized 5‐amino‐3,4‐dihydro‐2H‐pyrrole‐2‐carboxylic acid esters, starting from commercially available phenylsulfonylacetonitrile, aldehydes, and N‐(diphenylmethylene)glycine tert‐butyl ester, was developed. The one‐pot strategy delivered this class of amidines bearing, for the first time, three contiguous stereocenters, in good to high yield and diastereoselectivity. The entire sequence was carried out using diethyl carbonate and 2‐methyl tetrahydrofuran as benign solvents, operating under metal‐free conditions. The process could be conveniently scaled‐up, and the synthetic utility of the products was demonstrated.