Prebiotic Synthesis and Isomerization in Interstellar Analog Ice: Glycinal, Acetamide, and Their Enol Tautomers

Glycinal (HCOCH2NH2) and acetamide (CH3CONH2) are simple molecular building blocks of biomolecules in prebiotic chemistry, though their origin on early Earth and formation in interstellar media remain a mystery. These molecules are formed with their tautomers in low temperature interstellar model ices upon interaction with simulated galactic cosmic rays. Glycinal and acetamide are accessed via barrierless radical‐radical reactions of vinoxy (⋅CH2CHO) and acetyl (⋅C(O)CH3), and then undergo keto‐enol tautomerization. Exploiting tunable photoionization reflectron time‐of‐flight mass spectroscopy and photoionization efficiency (PIE) curves, these results demonstrate fundamental reaction pathways for the formation of complex organics through non‐equilibrium ice reactions in cold molecular cloud environments. These molecules demonstrate an unconventional starting point for abiotic synthesis of organics relevant to contemporary biomolecules like polypeptides and cell membranes in deep space. Out of the cold: Ammonia (NH3) and acetaldehyde (CH3CHO) are exposed to galactic cosmic ray proxies while frozen at 5 K to simulate the environment of an interstellar molecular cloud. Reactants undergo dissociation and radical recombination to produce glycinal (NH2CH2CHO) and acetamide (CH3CONH2) prior to tautomerization to 2‐aminoethenol (HOCHCHNH2) and 1‐aminoethenol (H2CC(OH)NH2), respectively.