Gel permeation chromatography of the solvent extractables isolated from a thermally treated glucose/L-proline mixture and sensory analysis of the fractions collected led to the discovery of the presence of "cooling" compounds in Maillard reactions. To characterize the key compounds imparting this cooling sensation to the oral cavity, a taste dilution analysis was performed by determining the taste threshold of reaction products in serial dilutions of HPLC fractions to select the most intense "cooling" compounds in the complex GPC fraction of the Maillard reaction mixture. Systematic (13)C-labeling experiments and GC-MS, LC-MS, and 1D- and 2D-NMR measurements, followed by synthesis, led to the unequivocal identification of 3-methyl-2-(1-pyrrolidinyl)-2-cyclopenten-1-one (3-MPC), 5-methyl-2-(1-pyrrolidinyl)-2-cyclopenten-1-one (5-MPC), and 2,5-dimethyl-4-(1-pyrrolidinyl)-3(2H)-furanone (DMPF) as the key compounds contributing the most to the cooling sensation. Although these structures were described earlier with regard to Maillard reactions, this is the first time that Maillard reaction products are reported to cause intense cooling sensations by degustation. Finally, the detection of 5-MPC (101.3 microg/kg), 3-MPC (9.4 microg/kg), and DMPF (11.5 microg/kg) in dark malt verified their natural occurrence in thermally processed foods.