Strobilurin

Last updated

Strobilurins are a group of natural products and their synthetic analogs. A number of strobilurins are used in agriculture as fungicides. They are part of the larger group of QoIs (Quinone outside Inhibitors), which act to inhibit the respiratory chain at the level of Complex III.

Contents

The first parent natural products, strobilurins A and B, were extracted from the fungus Strobilurus tenacellus . [1] Commercial strobilurin fungicides [2] were developed through optimization of photostability and activity. [3] Strobilurins represented a major development in fungus-based fungicides. First released in 1996, there are now ten major strobilurin fungicides on the market, which account for 23-25 % of the global fungicide sales. [4] Examples of commercialized strobilurin derivatives are azoxystrobin, kresoxim-methyl, picoxystrobin, fluoxastrobin, oryzastrobin, dimoxystrobin, pyraclostrobin and trifloxystrobin.

Strobilurins are mostly contact fungicides with a long half time as they are absorbed into the cuticle and not transported any further. They have a suppressive effect on other fungi, reducing competition for nutrients; they inhibit electron transfer in mitochondria, disrupting metabolism and preventing growth of the target fungi. [5]

Natural strobilurins

Strobilurin A

Strobilurin A.svg

Strobilurin A (also known as mucidin) is produced by Oudemansiella mucida , Strobilurus tenacellus , Bolinea lutea , and others. [6] [7] [8] When first isolated it was incorrectly assigned as the E E E geometric isomer but was later identified by total synthesis as being the E Z E isomer, as shown. [5] :694

9-Methoxystrobilurin A

9-Methoxystrobilurin A is produced by Favolaschia spp. [7]

Strobilurin B

Strobilurin B.svg

Strobilurin B is produced by S. tenacellus. [7]

Strobilurin C

Strobilurin C.svg

Strobilurin C is produced by X. longipes and X. melanotricha . [7] [8]

Strobilurin D and G

Strobilurin D.svg

Strobilurin D is produced by Cyphellopsis anomala . [8] Its structure was originally incorrectly assigned and is now considered to be identical to that of strobilurin G, produced by B. lutea. [7] [8] A related material, hydroxystrobilurin D, with an additional hydroxyl group attached to the methyl of the main chain is produced by Mycena sanguinolenta . [7]

Strobilurin E

Strobilurin E.svg

Strobilurin E is produced by Crepidotus fulvotomentosus [8] and Favolaschia spp. [7]

Strobilurin F2

Strobilurin F2.svg

Strobilurin F2 is produced by B. lutea. [6]

Strobilurin H

Strobilurin H.svg

Strobilurin H is produced by B. lutea. [7] The natural product with a phenolic hydroxy group in place of the aromatic methoxy group of strobilurin H is called strobilurin F1 and is found in C. anomala [8] and Agaricus spp. [6]

Strobilurin X

Strobilurin X.svg

Strobilurin X is produced by O. mucida. [7] [8]

Oudemansins

The oudemansins are closely related to the strobilurins and are also quinone outside inhibitors. [7]

Oudemansins general.svg

Oudemansin A with R1 = R2 = H was first described in 1979, after being isolated from mycelial fermentations of the basidiomycete fungus Oudemansiella mucida. [9] Later it was found in cultures of the basidiomycete fungi Mycena polygramma and Xerula melanotricha. The latter fungus also produces oudemansin B, with R1 = MeO and R2 = Cl. Oudemansin X, with R1 = H and R2 = MeO was isolated from Oudemansiella radicata . [6]

Synthetic strobilurins

The discovery of the strobilurin class of fungicides led to the development of a group of commercial fungicides used in agriculture. Examples are shown below. [5]

See also

Related Research Articles

Q<sub>o</sub>I Kind of chemicals used to kill fungus

Qo inhibitors (QoI), or quinone outside inhibitors, are a group of fungicides used in agriculture. Some of these fungicides are among the most popular in the world. QoI are chemical compounds which act at the quinol outer binding site of the cytochrome bc1 complex.

Fungicides are pesticides used to kill parasitic fungi or their spores. Fungi can cause serious damage in agriculture, resulting in critical losses of yield, quality, and profit. Fungicides are used both in agriculture and to fight fungal infections in animals. Fungicides are also used to control oomycetes, which are not taxonomically/genetically fungi, although sharing similar methods of infecting plants. Fungicides can either be contact, translaminar or systemic. Contact fungicides are not taken up into the plant tissue and protect only the plant where the spray is deposited. Translaminar fungicides redistribute the fungicide from the upper, sprayed leaf surface to the lower, unsprayed surface. Systemic fungicides are taken up and redistributed through the xylem vessels. Few fungicides move to all parts of a plant. Some are locally systemic, and some move upward. Most fungicides that can be bought retail are sold in liquid form, the active ingredient being present at 0.08% in weaker concentrates, and as high as 0.5% for more potent fungicides. Fungicides in powdered form are usually around 90% sulfur.

<span class="mw-page-title-main">Azoxystrobin</span> Chemical compound

Azoxystrobin is a broad spectrum systemic fungicide widely used in agriculture to protect crops from fungal diseases. It was first marketed in 1996 using the brand name Amistar and by 1999 it had been registered in 48 countries on more than 50 crops. In the year 2000 it was announced that it had been granted UK Millennium product status.

<span class="mw-page-title-main">Spalting</span> Any form of coloration caused by a fungal infection in the wood

Spalting is any form of wood coloration caused by fungi. Although primarily found in dead trees, spalting can also occur in living trees under stress. Although spalting can cause weight loss and strength loss in the wood, the unique coloration and patterns of spalted wood are sought by woodworkers.

<i>Mycena leaiana</i> Species of fungus

Mycena leaiana, commonly known as the orange mycena or Lea's mycena, is a species of saprobic fungi in the genus Mycena, family Mycenaceae. Characterized by their bright orange caps and stalks and reddish-orange gill edges, they usually grow in dense clusters on deciduous logs. The pigment responsible for the orange color in this species has antibiotic properties. A variety of the species, Mycena leaiana var. australis, can be found in Australia and New Zealand.

<span class="mw-page-title-main">Wolfgang Steglich</span> German chemist (born 1933)

Wolfgang Steglich is a German chemist.

<i>Mycena vitilis</i> Species of fungus

Mycena vitilis, commonly known as the snapping bonnet, is a species of inedible mushroom in the family Mycenaceae. It is found in Europe and North America, where it grows on the ground among leaves in damp places, especially under alder. The small pale gray to whitish fruit bodies are usually attached to small sticks buried in the leaves and detritus. They are distinguished by their long, slender stems that root into the ground, and by the grooved cap that reaches diameters of up to 2.2 cm (0.9 in). The grayish-white gills on the underside of the cap are distantly spaced, and adnately attached to the stem. M. vitilis contains strobilurin B, a fungicidal compound with potential use in agriculture.

<i>Mycena sanguinolenta</i> Species of fungus

Mycena sanguinolenta, commonly known as the bleeding bonnet, the smaller bleeding Mycena, or the terrestrial bleeding Mycena, is a species of mushroom in the family Mycenaceae. It is a common and widely distributed species, and has been found in North America, Europe, Australia, and Asia. The fungus produces reddish-brown to reddish-purple fruit bodies with conic to bell-shaped caps up to 1.5 cm (0.6 in) wide held by slender stipes up to 6 cm (2.4 in) high. When fresh, the fruit bodies will "bleed" a dark reddish-purple sap. The similar Mycena haematopus is larger, and grows on decaying wood, usually in clumps. M. sanguinolenta contains alkaloid pigments that are unique to the species, may produce an antifungal compound, and is bioluminescent. The edibility of the mushroom has not been determined.

<i>Pterula</i> Genus of fungi

Pterula is a genus of fungi in the Pterulaceae family. The genus has a widespread distribution, especially in tropical regions, and contains about 50 species. One such species, Pterula sp. 82168, has yielded potential antifungal antibiotic properties.

<i>Galiella rufa</i> Species of fungus

Galiella rufa, commonly known as the rubber cup, the rufous rubber cup, or the hairy rubber cup, is a species of fungus in the family Sarcosomataceae. It produces cup-shaped fruit bodies with the texture of tough, gelatinous rubber, with a rough, blackish-brown, felt-like outer surface and a smooth reddish-brown inner surface.

<i>Strobilurus tenacellus</i> Species of fungus

Strobilurus tenacellus, commonly known as the pinecone cap, is a species of agaric fungus in the family Physalacriaceae. It is found in Asia and Europe, where it grows on the fallen cones of pine and spruce trees. The fruit bodies (mushrooms) are small, with convex to flat, reddish to brownish caps up to 15 mm (0.6 in) in diameter, set atop thin cylindrical stems up to 4–7.5 cm (1.6–3.0 in) long with a rooting base. A characteristic microscopic feature of the mushroom is the sharp, thin-walled cystidia found on the stipe, gills, and cap. The mushrooms, sometimes described as edible, are too small to be of culinary interest. The fungus releases compounds called strobilurins that suppress the growth and development of other fungi. Derivatives of these compounds are used as an important class of agricultural fungicides.

<span class="mw-page-title-main">Variegatic acid</span> Chemical compound

Variegatic acid is an orange pigment found in some mushrooms. It is responsible for the bluing reaction seen in many bolete mushrooms when they are injured. When mushroom tissue containing variegatic acid is exposed to air, the chemical is enzymatically oxidized to blue quinone methide anions, specifically chinonmethid anions. It is derived from xerocomic acid, which is preceded by atromentic acid and atromentin, and its genetic basis is unknown. In its oxidized form is variegatorubin, similar to xerocomorubin.

<i>Mycena purpureofusca</i> Species of fungus

Mycena purpureofusca, commonly known as the purple edge bonnet, is a species of agaric fungus in the family Mycenaceae. First described by Charles Horton Peck in 1885, the species is found in Europe and North America, where it grows on the decaying wood and debris of conifers, including cones. Fruit bodies have conical to bell-shaped purple caps up to 2.5 cm (1 in) set atop slender stipes up to 10 cm (4 in) long. The mushroom is named for the characteristic dark greyish-purple color of its gill edges. In the field, M. purpureofusca mushrooms can usually be distinguished from similar species by characteristics such as the dark purple gill edges, the deep purple cap center, and its cartilagineous consistency. The fungus contains a laccase enzyme that has been investigated scientifically for its potential to detoxify recalcitrant industrial dyes used in textile dyeing and printing processes.

<i>Oudemansiella mucida</i> Species of basidiomycete fungus

Oudemansiella mucida, commonly known as porcelain fungus, is a basidiomycete fungus of the family Physalacriaceae and native to Europe.

<span class="mw-page-title-main">Oudemansin A</span> Chemical compound

Oudemansin A is a natural product first isolated from the basidiomycete fungus Oudemansiella mucida. Its chemical structure was determined by X-ray crystallography in 1979 and absolute stereochemistry by total synthesis. Two closely related derivatives, oudemansin B and X have also been isolated from other basidiomycetes. They are all biologically active against many filamentous fungi and yeasts but with insufficient potency and stability to become useful commercial products. However, their discovery, together with the strobilurins led to agricultural fungicides including azoxystrobin with the same mechanism of action.

Fungal isolates have been researched for decades. Because fungi often exist in thin mycelial monolayers, with no protective shell, immune system, and limited mobility, they have developed the ability to synthesize a variety of unusual compounds for survival. Researchers have discovered fungal isolates with anticancer, antimicrobial, immunomodulatory, and other bio-active properties. The first statins, β-Lactam antibiotics, as well as a few important antifungals, were discovered in fungi.

Medicinal fungi are fungi that contain metabolites or can be induced to produce metabolites through biotechnology to develop prescription drugs. Compounds successfully developed into drugs or under research include antibiotics, anti-cancer drugs, cholesterol and ergosterol synthesis inhibitors, psychotropic drugs, immunosuppressants and fungicides.

<span class="mw-page-title-main">Fluxapyroxad</span> Chemical compound

Fluxapyroxad is a broad-spectrum pyrazole-carboxamide fungicide used on a large variety of commercial crops. It stunts fungus growth by inhibiting the succinate dehydrogenase (SQR) enzyme. Application of fluxapyroxad helps prevent many wilts and other fungal infections from taking hold. As with other systemic pesticides that have a long chemical half-life, there are concerns about keeping fluxapyroxad out of the groundwater, especially when combined with pyraclostrobin. There is also concern that some fungi may develop resistance to fluxapyroxad.

<span class="mw-page-title-main">Pyraclostrobin</span> Agricultural fungicide, QoI, strobilurin

Pyraclostrobin is a quinone outside inhibitor (QoI)-type fungicide used in agriculture. Among the QoIs, it lies within the strobilurin chemical class.

References

  1. Schramm, Georg; Steglich, Wolfgang; Anke, Timm; Oberwinkler, Franz (1978). "Antibiotika aus Basidiomyceten, III. Strobilurin a und B, antifungische Stoffwechselprodukte aus Strobilurus tenacellus". Chemische Berichte. 111 (8): 2779–2784. doi:10.1002/cber.19781110806.
  2. Peter Jeschke, Matthias Witschel, Wolfgang Krämer, Ulrich Schirmer (eds.): Modern Crop Protection Compounds, 3rd edition, Wiley-VCH, 2019, ISBN   978-3-527-34089-7.
  3. Sauter, Hubert; Steglich, Wolfgang; Anke, Timm (1999). "Strobilurins: Evolution of a New Class of Active Substances". Angewandte Chemie International Edition. 38 (10): 1328–1349. doi:10.1002/(SICI)1521-3773(19990517)38:10<1328::AID-ANIE1328>3.0.CO;2-1. PMID   29711574.
  4. Juliet D. Tang, Tina Ciaramitaro, Maria Tomaso-Peterson, Susan V. Diehl (2017). "Activity of Two Strobilurin Fungicides Against Three Species of Decay Fungi in Agar Plate Tests". Proc. IRG Annual Meeting: IRG/WP 17-30704.{{cite journal}}: CS1 maint: multiple names: authors list (link) (pdf link)
  5. 1 2 3 Schaefer, Bernd (2014). "Agrochemicals: 8.2 Strobilurins". Natural Products in the Chemical Industry. pp. 688–704. doi:10.1007/978-3-642-54461-3_8. ISBN   978-3-642-54460-6.
  6. 1 2 3 4 Lorenzen, K.; Anke, T. (1998). Mori, Kenji (ed.). "Basidiomycetes as a Source for New Bioactive Natural Products". Current Organic Chemistry. 2 (4). Bentham Science Publishers: 329–364. doi:10.2174/1385272802666220128213627. ISSN   1385-2728. S2CID   246934805.
  7. 1 2 3 4 5 6 7 8 9 10 Anke, T.; Erkel, G. (2002). "Non-β-Lactam Antibiotics". Industrial Applications. pp. 101–104. doi:10.1007/978-3-662-10378-4_5. ISBN   978-3-642-07481-3.
  8. 1 2 3 4 5 6 7 Zakharychev, Vladimir V; Kovalenko, Leonid V (1998-06-30). "Natural compounds of the strobilurin series and their synthetic analogues as cell respiration inhibitors". [ Russian Chemical Reviews ] (Успехи химии). 67 (6). IOP Publishing: 535–544. Bibcode:1998RuCRv..67..535Z. doi:10.1070/rc1998v067n06abeh000426. ISSN   0036-021X. S2CID   95676421.
  9. Anke, Timm; Hecht, Hans Jürgen; Chramm, Georgs; Steglich, Wolfgang (1979). "Antibiotics from basidiomycetes. IX. Oudemansin, an antifungal antibiotic from Oudemansiella mucida (Schrader ex Fr.) hoehnel (Agaricales)". The Journal of Antibiotics. 32 (11): 1112–1117. doi: 10.7164/antibiotics.32.1112 . PMID   528381.