Nonproteinogenic Amino Acid

Nonproteinogenic amino acids, NAAs, are widely produced by bacteria, animals, and plants for purposes beyond building proteins. Oxyvinylglycines are a unique family of NAAs featuring a core vinyl ether moiety. This moiety is essential for the antimicrobial activity and agrichemical application of oxyvinylglycines, but the biosynthetic chemistries for the vinyl ether have remained unknown.

In work published in Angewandte Chemie, The Li Group reports the in vitro biosynthesis of the oxyvinylglycine L‐2‐amino‐4‐methoxy‐trans‐3‐butenoic acid, AMB. AMB is synthesized from glutamate as an alanyl‐AMB dipeptide using the N-terminal alanine as a protecting group.

Crafting the AMB vinyl ether requires a cascade of modifications, including a cryptic hydroxylation and a likely 2,3‐dehydration. Li’s study provides mechanistic understandings for the AMB biosynthetic pathway and sets the stage for identifying new vinyl ether-containing natural products.