Amino acids and their
derivatives were probably instrumental in
the transition of prebiotic chemistry to early biology. Accordingly,
amino acid formation under prebiotic conditions has been intensively
investigated. Unsurprisingly, most of these studies have taken place
with water as the solvent. Herein, we describe an investigation into
the formation and subsequent reactions of aminonitriles and their
formylated derivatives in formamide. We find thatN-formylaminonitriles form readily from aldehydes and cyanide in formamide,
even in the absence of added ammonia, suggesting a potentially prebiotic
source of amino acid derivatives. Alkaline processing ofN-formylaminonitriles proceeds with hydration at the nitrile group
faster than deformylation, protecting aminonitrile derivatives from
reversion of the Strecker condensation equilibrium during hydration/hydrolysis
and furnishing mixtures of N-formylated and unformylated amino acid
derivatives. Furthermore, the facile synthesis ofN-formyldehydroalanine nitrile is observed in formamide from glycolaldehyde
and cyanide without intervention. Dehydroalanine derivatives have
been proposed as important compounds for prebiotic peptide synthesis,
and we demonstrate both a synthesis suggesting that they are potentially
plausible components of a prebiotic inventory, and reactions showing
their utility as abiotic precursors to a range of compounds of prebiological
interest.