Formation of Pyrrolnitrin and 3‐(2‐Amino‐3‐chlorophenyl)pyrrole from 7‐Chlorotryptophan

Abstract

Little is known about chlorinations in secondary metabolism. In connection with the biosynthesis of the antifungal antibiotic pyrrolnitrin (2), NO2 in place of NH2, the metabolite (2) has now been isolated for the first time. The intermediates (1) and (3) were elucidated on a previous occasion.

Identification and Characterization of the Flavin:NADH Reductase (PrnF) Involved in a Novel Two-Component Arylamine Oxygenase

“…In the proposed biosynthetic pathway of pyrrolnitrin ( Fig. 1), PrnD catalyzes the oxidation of the amino group of aminopyrrolnitrin to a nitro group, forming pyrrolnitrin (41). In addition, we have obtained direct evidence for the involvement of hydroxylamine and nitroso intermediates in the PrnD-catalyzed arylamine oxygenation reaction, substantiating a two-component monooxygenase-type catalytic mechanism for the conversion of arylamine to arylnitro compounds (24).…”

“…2), including four open reading frames (ORFs) (prnA to -D), which have been previously described as a complete operon for pyrrolnitrin biosynthesis (14,41). All ORFs were in the same orientation from prnA (the first ORF) to the eighth ORF.…”

Probing the Substrate Specificity of Aminopyrrolnitrin Oxygenase (PrnD) by Mutational Analysis

“…PrnD is involved in the biosynthesis of the antibiotic pyrrolnitrin, which is produced by many pseudomonads and has broadspectrum antifungal activity (1,5,12,18). In the proposed biosynthetic pathway of pyrrolnitrin, PrnD catalyzes the oxidation of the amino group of aminopyrrolnitrin (Aprn) to a nitro group, forming pyrrolnitrin (22). Arylamine oxygenases seem to be widespread and are used in diverse metabolic reactions (6,11,13,16,17,19).…”

Reconstitution and Characterization of Aminopyrrolnitrin Oxygenase, a Rieske N-Oxygenase That Catalyzes Unusual Arylamine Oxidation

“…This DNA region confers the ability to produce pyrrolnitrin when expressed heterologously in Escherichia coli and contains four genes, prnABCD, each of which is required for pyrrolnitrin production (9). A hypothetical biochemical pathway for the synthesis of pyrrolnitrin has been proposed by van Pée et al (10). In this pathway shown in Fig.…”