Pseudomonas pyrrocinia

Nonheme/ Bacterium Pseudomonas pyrrocinia, Cl, Br, Wiesner et al. (1988), Weng et al. 

Wiesner W, K-H van Pee, F Lingens (1988) Purification and characterization of a novel non-heme chloroperoxidase from Pseudomonas pyrrocinia. J Biol Chem 263 13725-13732. 

In Pseudomonas pyrrocinia, transformation was initiated by oxidation of the side chain to indole-3-acetate that was further degraded to indole-3-carboxylate before decarboxylation to indole (Figure 10.3c) (Liibbe et al. 1983). 

Lubbe C, K-H van Pee, O Salcher, F Lingens (1983) The metabolism of tryptophan and 7-chlorotryptophan in Pseudomonas pyrrocinia and Pseudomonas aureofaciens. Zphysiol Chem 364 447-453. 

Furthermore, the preparation of the antibiotic Pyrrolnitrine by oxidation of the amino-functionalized precursor with the chloroperoxidase from Pseudomonas pyrrocinia was reported (Eq. 13) [155]. The mechanism of this peroxidase-catalyzed N-oxidation has not been elucidated. 

A remarkable, intriguing rearrangement that possibly eould be framed in the context of this ehapter is the one observed in the biosynthesis of the chlorinated fungicide pyrrolnitrin. This compound is produced from the amino aeid tryptophan 179 by the baeterial cells of Pseudomonas pyrrocinia [85BBA181 91MI2 92MI1 94MI3]. A proposal for the biosynthesis... 

Other peroxidases, albeit non-heme, are able to catalyze similar oxidations. CPO from Pseudomonas pyrrocinia has been successfully employed for the preparation of the antibiotic pyrrolnitrine [60]. The amino group of the precursor molecule is directly transformed into a nitro group by the CPO active species (Fig. 6.4b). 

Wiesner W, van Pee KH, Lingens F (1986) Detection of a new chloroperoxidase in Pseudomonas pyrrocinia. FEBS Lett 209 321-324... 

The phenylpyrrole class of fungicides includes the conq>ounds fenpiclonil and fludioxo-nil. These chemistries have been developed fix>m the natural product lead molecule pyr-rolnitrin produced by Pseudomonas pyrrocinia (Fig. 3). The photoinstability of pyrrol-nitrin was overcome in the synthetic analogs and these compounds are now used for the control of Botrytis cinerea, Monilinia, and Sclerotinia spp. [12]. 

Perhydrolase (non-heme, non-metal) Pseudomonas pyrrocinia indole (Cl-, Br-) 29... 

The antifungal antibiotic pyrrolnitrin [3-chloro-4-(2-nitro-3-chlorophenyl)pyrrole] was brominated at the 2-position of the pyrrole moiety by bromoperoxidase from Streptomyces phaeochromogenes. Pyrrolnitrin was chlorinated at the 2-position and at the 2,5-positions of the pyrrole system by perhydrolases from Pseudomonas pyrrocinia and Streptomyces aureofaciens. The corresponding bromo-derivatives were also obtained with these enzymes f54f... 

Another phenylpyrrole compound, 2-(3,5-dibromo-2-methoxyphenyl)pyrrole was brominated to 2-bromo-, 2,3-dibromo-, 3,4-dibromo-, 2,3,4-tribromo-5-(3,5-dibromo-2-methoxyphenyl) pyrrole by perhydrolase from Streptomyces aureofaciens Tu241551. When the same substrate was chlorinated using the perhydrolases from Pseudomonas pyrrocinia and Streptomyces aureofaciens Tii24, 2-chloro-, 3-chloro-, 4-chloro-, 2,3-dichloro-, 2,4-dichloro, and 3,4-dichloro-5-(3,5-dibromo-2-methoxyphenyl)pyr-role could be isolated (Fig. 16.9-5)[56]. 

Saphire , Syngenta) [164] have been developed from the photo-unstable and chlorine-containing natural antibiotic pyrrolnitrin (75 Pyroace , Fujisawa) that was first isolated from Pseudomonas pyrrocinia [165] (Fig. 35.18, Table 35.11). 

Pyrrolnitrin (137) and 3-chloroindole (138) are two products of tryptophan metabolism in Pseudomonas pyrrocinia and Pseudomonas aureofaciens °. The occurrence of phenylpyrrole compounds in nature is rare and it has been suggested that the antifungal compound pyrrolnitrin (137) is produced from tryptophan in a reaction initiated by a chloroperoxidase system Figure 4.21). 

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