The aza-Michael addition reaction represents one of the most powerful methods for the formation of carbon-nitrogen bonds in organic synthesis. Thanks to the fast addition of the amine on the ethylene sites of the glycerol carbonate acrylate permitting the aza-Michael reaction to occur first. Significant methods have been studied to monitor the addition reaction of the amine on glycerol carbonate acrylate. New five-membered cyclic glycerylic carbonate (5CGC) and hydroxyurethane isomers were synthesized under solvent free reaction conditions, short reaction times, and without the use of expensive catalysts. These new molecules, enriched with ester and amine functions, provided novel and more environmentally friendly synthons for the synthesis of bio-based polyhydroxyurethanes without the use of phosgene or isocyanate.