enterocin

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| Name = Enterocin

| ImageFile = Enterocin.png

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| OtherNames = Vulgamycin

| IUPACName = (10S)-2-benzoyl-1,3,8,10-tetrahydroxy-9-(4-methoxy-6-oxopyran-2-yl)-5-oxatricyclo[4.3.1.03,8]decan-4-one

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| CASNo = 59678-46-5

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| PubChem = 10478614

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| ChemSpiderID = 19978603

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| SMILES = COC1=CC(=O)OC(=C1)C2C3(CC4C(C2(C(C3(C(=O)O4)O)C(=O)C5=CC=CC=C5)O)O)O

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| StdInChI = InChI=1S/C22H20O10/c1-30-11-7-12(31-14(23)8-11)16-20(27)9-13-18(25)21(16,28)17(22(20,29)19(26)32-13)15(24)10-5-3-2-4-6-10/h2-8,13,16-18,25,27-29H,9H2,1H3/t13?,16?,17?,18-,20?,21?,22?/m0/s1

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| StdInChIKey = CTBBEXWJRAPJIZ-LXJDDUSDSA-N }}

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| C=22 | H=20 | O=10

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Enterocin and its derivatives are bacteriocins synthesized by the lactic acid bacteria, Enterococcus. This class of polyketide antibiotics are effective against foodborne pathogens including L. monocytogenes, Listeria, and Bacillus.{{cite journal | vauthors = Khan H, Flint S, Yu PL | title = Enterocins in food preservation | journal = International Journal of Food Microbiology | volume = 141 | issue = 1–2 | pages = 1–10 | date = June 2010 | pmid = 20399522 | doi = 10.1016/j.ijfoodmicro.2010.03.005 }} Due to its proteolytic degradability in the gastrointestinal tract, enterocin is used for controlling foodborne pathogens via human consumption.{{Cite book | vauthors = Singh A, Walia D, Batra N |date=2018-01-01 | chapter = Fresh-Cut Fruits: Microbial Degradation and Preservation | title = Microbial Contamination and Food Degradation |pages=149–176|doi=10.1016/B978-0-12-811515-2.00006-8 | isbn = 978-0-12-811515-2 }}

History

Enterocin was discovered from soil and marine Streptomyces{{cite journal | vauthors = Miyairi N, Sakai H, Konomi T, Imanaka H | title = Enterocin, a new antibiotic taxonomy, isolation and characterization | journal = The Journal of Antibiotics | volume = 29 | issue = 3 | pages = 227–35 | date = March 1976 | pmid = 770404 | doi = 10.7164/antibiotics.29.227 | doi-access = free }} strains as well as from marine ascidians of Didemnum{{Cite journal| vauthors = Kang H, Jensen PR, Fenical W |date=1996|title=Isolation of Microbial Antibiotics from a Marine Ascidian of the GenusDidemnum|url=https://pubs.acs.org/doi/pdf/10.1021/jo951794g|journal=The Journal of Organic Chemistry|volume=61|issue=4|pages=1543–1546|doi=10.1021/jo951794g|issn=0022-3263|url-access=subscription}} and it has also been found in a mangrove strains Streptomyces qinglanensis and Salinispora pacifica.{{cite journal | vauthors = Bonet B, Teufel R, Crüsemann M, Ziemert N, Moore BS | title = Direct capture and heterologous expression of Salinispora natural product genes for the biosynthesis of enterocin | journal = Journal of Natural Products | volume = 78 | issue = 3 | pages = 539–42 | date = March 2015 | pmid = 25382643 | pmc = 4380194 | doi = 10.1021/np500664q }}

Total synthesis

The total synthesis of enterocin has been reported.{{cite journal | vauthors = Rizzo A, Trauner D | title = Toward (-)-Enterocin: An Improved Cuprate Barbier Protocol To Overcome Strain and Sterical Hindrance | journal = Organic Letters | volume = 20 | issue = 7 | pages = 1841–1844 | date = April 2018 | pmid = 29553746 | doi = 10.1021/acs.orglett.8b00353 }}

Biosynthesis

Enterocin has a caged, tricyclic, nonaromatic core and its formation undergoes a flavoenzyme (EncM) catalyzed Favorskii-like rearrangement of a poly(beta-carbonyl).{{cite journal | vauthors = Teufel R, Miyanaga A, Michaudel Q, Stull F, Louie G, Noel JP, Baran PS, Palfey B, Moore BS | display-authors = 6 | title = Flavin-mediated dual oxidation controls an enzymatic Favorskii-type rearrangement | journal = Nature | volume = 503 | issue = 7477 | pages = 552–556 | date = November 2013 | pmid = 24162851 | pmc = 3844076 | doi = 10.1038/nature12643 | bibcode = 2013Natur.503..552T }} Studies done on enterocin have shown that it is biosynthesized from a type II polyketide synthase (PKS) pathway, starting with a structure derived from phenylalanine or activation of benzoic acid followed by the EncM catalyzed rearrangement.

File:Enterocin biosynthesis.png

The enzyme EncN catalyzes the ATP-dependent transfer of the benzoate to EncC, the acyl carrier protein. EncC transfers the aromatic unit to EncA-EncB, the ketosynthase in order for malonation via FabD, the malonyl-CoA:ACP transacylase. A Claisen condensation occurs between the benzoyl and malonyl groups and occurs six more times followed by reaction with EncD, a ketoreductase; the intermediate undergoes the EncM catalyzed oxidative rearrangement to form the enterocin tricyclic core. Further reaction with O-methyltransferase, EncK and cytochrome P450 hydroxylase, EncR yields enterocin.{{cite journal | vauthors = Kalaitzis JA, Cheng Q, Thomas PM, Kelleher NL, Moore BS | title = In vitro biosynthesis of unnatural enterocin and wailupemycin polyketides | journal = Journal of Natural Products | volume = 72 | issue = 3 | pages = 469–72 | date = March 2009 | pmid = 19215142 | pmc = 2765504 | doi = 10.1021/np800598t }}

References