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Literature summary extracted from

  • Mahmoodi, N.; Qian, Q.; Luk, L.; Tanner, M.
    Rearrangements in the mechanisms of the indole alkaloid prenyltransferases (2013), Pure Appl. Chem., 85, 1935-1948.
No PubMed abstract available

Protein Variants

EC Number Protein Variants Comment Organism
2.5.1.34 K174A mutation of active site catalytic residue Lys174 to Ala results in a 20fold drop in the value of kcat, the Lys174Ala produces an unusual reverse-prenylated product, 3a-(2-methylbut-3-en-2-yl)-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b]indole-2-carboxylic acid Aspergillus fumigatus

Natural Substrates/ Products (Substrates)

EC Number Natural Substrates Organism Comment (Nat. Sub.) Natural Products Comment (Nat. Pro.) Rev. Reac.
2.5.1.34 dimethylallyl diphosphate + L-tryptophan Aspergillus fumigatus
-
diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan
-
?
2.5.1.106 dimethylallyl diphosphate + brevianamide F Aspergillus fumigatus i.e. cyclo-L-Trp-L-Pro diphosphate + tryprostatin B
-
?

Organism

EC Number Organism UniProt Comment Textmining
2.5.1.34 Aspergillus fumigatus Q50EL0 gene 4-DMATS
-
2.5.1.106 Aspergillus fumigatus
-
-
-

Reaction

EC Number Reaction Comment Organism Reaction ID
2.5.1.34 dimethylallyl diphosphate + L-tryptophan = diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan SN1-like mechanism involving a discrete carbocation intermediate involving initial ion pair formation followed by a reverse prenylation at the nucleophilic C-3 position, detailed overview Aspergillus fumigatus

Substrates and Products (Substrate)

EC Number Substrates Comment Substrates Organism Products Comment (Products) Rev. Reac.
2.5.1.34 dimethylallyl diphosphate + L-tryptophan
-
Aspergillus fumigatus diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan
-
?
2.5.1.34 dimethylallyl diphosphate + L-tryptophan the enzyme prenylates the non-nucleophilic C-4 position of the indole ring in free tryptophan Aspergillus fumigatus diphosphate + 4-(3-methylbut-2-enyl)-L-tryptophan
-
?
2.5.1.106 dimethylallyl diphosphate + brevianamide F i.e. cyclo-L-Trp-L-Pro Aspergillus fumigatus diphosphate + tryprostatin B
-
?
2.5.1.106 additional information comparison of mechanisms of the indole alkaloid prenyltransferases. Tryprostatin B synthase catalyzes the normal C-2 prenylation of the indole ring in brevianamide F (cyclo-L-Trp-L-Pro). Mechanism includes an initial C-3 prenylation (either normal or reverse) followed by carbo cation rearrangements to give product Aspergillus fumigatus ?
-
?

Synonyms

EC Number Synonyms Comment Organism
2.5.1.34 4-DMATS
-
Aspergillus fumigatus
2.5.1.34 FgaPT2
-
Aspergillus fumigatus
2.5.1.106 FtmPT1
-
Aspergillus fumigatus
2.5.1.106 tryprostatin B synthase
-
Aspergillus fumigatus

General Information

EC Number General Information Comment Organism
2.5.1.34 evolution 4-DMATS follows a mechanism that involves initial ion pair formation followed by a reverse prenylation at the nucleophilic C-3 position. Generation of the C-4 normal prenylated intermediate and deprotonation rearomatizes the indole ring. The enzyme tryprostatin B synthase (FtmPT1) catalyzes the normal C-2 prenylation of the indole ring in brevianamide F (cyclo-L-Trp-L-Pro). It shares high structural homology with 4-DMATS, and catalyzes a reaction in favor of an initial C-3 prenylation (either normal or reverse) followed by carbo cation rearrangements to give product. The concept of a common intermediate that partitions to different products via rearrangements can help to explain how these evolutionarily related enzymes can prenylate different positions on the indole ring Aspergillus fumigatus
2.5.1.34 additional information key active site residues are Glu89 and Lys174 Aspergillus fumigatus