Organic carbonates(OCs)are a class of compounds featured by a carbonyl flanked by two alkoxy/aryloxy groups.They exist in either linear or cyclic forms,of which the majority encountered in nature adopt a pentacyclic structure.However,the enzymatic basis for pentacyclic carbonate ring for-mation remains elusive.Here,we reported that a four-protein metabolon(AlmUII-UV)assembled by a small peptide protein(AlmUV)appends a reactive N-hydroxylcarbamoyl moiety to the decarboxylated aldgamycins followed by a non-enzymatic condensation to give the pentacyclic carbonate ring.Our re-sults have documented an unprecedent mechanism for carbonate formation.