The exploration of interstellar media (ISM) and meteorites has unveiled a rich array of complex organic molecules, encompassing amino acids, 1 sugars, 2 purine bases, and short peptides. The identification of over 300 distinct compounds has spurred investigations into the origins of life and the fundamental chemical processes involved. Under the challenging conditions of the interstellar medium (ISM), characterized by low temperatures and high dilution, the formation of highly reactive species becomes essential for prebiotic organic reactions. These involve activating thermodynamically stable small molecules, such as CO, CO2, H2O, CH4, HCN, formaldehyde, simple alcohols, and various carboxylic acids. While our understanding of organic chemistry thrives in controlled (wet) laboratory environments, it faces limitations when extending into the much less wellunderstood conditions of the ISM. One challenging aspect is that the energy for initiating chemical reactions often is concentrated in terms of time and space, and is primarily provided by stellar energy beams. Hence, high-energy isomers of thermodynamically very stable molecules play a crucial role in the formation of biologically relevant compounds. The remarkable discovery of glycolaldehyde only in the year 2000 represents such a molecule. Its proposed formation mechanism, suggested in 2018, involves the higher energy tautomer of formaldehyde, hydroxymethylene (H-CO -OH), engaging in a highly facile, lowbarrier process (ΔH ≠ ≈1 kcal mol -1 ) with H2CO, even at the extremely low average temperature of space (~2.7 K). Enols are considered crucial intermediates in the organic chemistry in space and several enol tautomers have been identified in the ISM. For instance, the simplest enol, vinyl alcohol (CH2=CHOH), was discovered in the analysis of microwave emissions from Sagittarius B2.35 in 2001. The gas phase stability of enols has also been validated through laboratory experiments, including those involving the enols of acetamide, 24 acetic acid, glycolic acid, glycolaldehyde, and propionic acid. In solution, enols display high reactivity and isomerize rapidly into the more thermodynamically more stable keto tautomers through bimolecular acid-base reactions. In the gas phase, however, enols are considerably more stable due to significant energy barriers (ranging from 40 to 45 kcal mol -1 ) 30-31 for [1,3]H-shifts. Consequently, enols can endure as long-lasting entities in the gas phase or in cold matrices. 30 Scheme 1. 2-Methyl-prop-1-ene-1,1-diol (2) generated from dimethylmalonic acid (1) through pyrolysis and trapping in an argon matrix. Subsequent photorearrangement to isobutyric acid (3) and dimethylketene (4) as well as the photorearrangement of 4 to propene (5).