Bottom-Up Synthesis of 1,1-Ethenediol (H 2 CC(OH) 2 )─The Simplest Unsaturated Geminal Diol─In Interstellar Analogue Ices.

Because of their nucleophilic character and high reactivity, enols─reaction intermediates carrying a hydroxyl group connected to a carbon-carbon double bond─play a key role in the formation of complex organic molecules in astrobiology and biochemistry. Here, we report the first bottom-up preparation of 1,1-ethenediol (H 2 CC(OH) 2 )─the simplest unsaturated geminal enol of acetic acid (CH 3 COOH) and potential precursor for the formation of glycine─in interstellar analogue ices of carbon dioxide and methane processed by proxies of galactic cosmic rays. These enols can easily form via nonequilibrium chemistry in low temperature (10 K) interstellar ices at abundances orders of magnitude higher than thermodynamically predicted. These energetically less favorable tautomers remain stable in ice-coated interstellar nanoparticles in molecular clouds and also upon sublimation into the gas phase in star forming regions thus providing the raw material to a complex and exotic organic chemistry under extreme conditions in deep space.