Dataset Information

In Vitro Biosynthesis of the Nonproteinogenic Amino Acid Methoxyvinylglycine.

ABSTRACT: Oxyvinylglycines are a family of nonproteinogenic amino acids featuring an essential vinyl ether conferring mechanism-based inhibition of pyridoxal phosphate enzymes. The gene clusters for a few oxyvinylglycines are known, yet the biosynthetic origin of the vinyl ether is elusive. The?in vitro biosynthesis of methoxyvinylglycine or l-2-amino-4-methoxy-trans-3-butenoic acid (AMB) is reported. It is shown that AMB is made from glutamate as an alanyl-AMB dipeptide and the rationale is provided for the N-term Ala. Using a chemical capture method, the order and timing of the modifications on non-ribosomal peptide synthetase (NRPS)-bound substrates was determined, including a cryptic hydroxylation of the Glu ?-carbon. Eliminating this hydroxy group likely generates a key ?,?-dehydroamino acid intermediate that facilitates decarboxylation. This work sheds light on vinyl ether biosynthesis and uncovers new NRPS chemistry.

SUBMITTER: Patteson JB

PROVIDER: S-EPMC6180322 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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In Vitro Biosynthesis of the Nonproteinogenic Amino Acid Methoxyvinylglycine.

Patteson Jon B JB Dunn Zachary D ZD Li Bo B

Angewandte Chemie (International ed. in English) 20180508 23

Oxyvinylglycines are a family of nonproteinogenic amino acids featuring an essential vinyl ether conferring mechanism-based inhibition of pyridoxal phosphate enzymes. The gene clusters for a few oxyvinylglycines are known, yet the biosynthetic origin of the vinyl ether is elusive. The in vitro biosynthesis of methoxyvinylglycine or l-2-amino-4-methoxy-trans-3-butenoic acid (AMB) is reported. It is shown that AMB is made from glutamate as an alanyl-AMB dipeptide and the rationale is provided for ...[more]

PMID: 29633497

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Dataset Information

In Vitro Biosynthesis of the Nonproteinogenic Amino Acid Methoxyvinylglycine.

Publications

In Vitro Biosynthesis of the Nonproteinogenic Amino Acid Methoxyvinylglycine.

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