79755-69-4Relevant academic research and scientific papers
Citrinin revisited: From monomers to dimers and beyond
Clark, Benjamin R.,Capon, Robert J.,Lacey, Ernest,Tennant, Shaun,Gill, Jennifer H.
, p. 1520 - 1528 (2008/02/03)
Detailed chemical analysis of the solid phase fermentation of an Australian Penicillium citrinum isolate has returned the known compounds citrinin (1), phenol A acid (6), dihydrocitrinone (7) and dihydrocitrinin (8), together with a novel cytotoxic dimer, dicitrinin A (5). Dicitrinin A (5) was determined to be a dimerised artefact of the major co-metabolite citrinin, and its structure solved by spectroscopic analysis and chemical modification. Analysis of the products encountered during the controlled decomposition of citrinin led to the discovery of additional citrinin dimers and delineated a plausible mechanistic pathway linking all monomeric and dimeric citrinin degradation products. The Royal Society of Chemistry 2006.
A major decomposition product, citrinin H2, from citrinin on heating with moisture.
Hirota, Mitsuru,Mehta, Alka,Yoneyama, Keiko,Kitabatake, Naofumi
, p. 206 - 210 (2007/10/03)
Citrinin is one of the mycotoxins produced by Penicillium citrinum. We examined the decomposition products after heating citrinin in water at 140 degrees C and isolated a major product, citrinin H2 (3-(3,5-dihydroxy-2-methylphenyl)-2-formyloxy-butane). Ci
Enantioselective Synthesis of the Polyketide Antibiotic (3R,4S)-(-)-Citrinin
Roedel, Thomas,Gerlach, Hans
, p. 885 - 888 (2007/10/02)
The fungal metabolite (-)-citrinin (1) was synthesized for the first time.Reaction of the Grignard reagent of 2,4-bis(benzyloxy)-6-bromotoluene (3) with (2S)-trans-(-)-2,3-dimethyloxirane (6) in the presence of 1,5-cyclooctadienecopper(I) chloride as catalyst leads to the formation of (2S,3S)-(-)-7 with erythro configuration.Compound (-)-7 could be transformed into (2R,3S)-(-)-9 with threo configuration via the formate (1R,2S)-(+)-8 by a Mitsunobu reaction.Reaction of the Grignard reagent of 3 with the achiral cis-2,3-dimethyl-oxirane yielded directly (+/-)-9.The starting material 3 was readily available from 1,3-bis(benzyloxy)-5-bromobenzene (4).Formylation of 4 furnished the aldehyde 5 which could be reduced to 3 with borane.Hydrogenolysis of the benzyl ether groups in (-)-9 gave (-)-2 with threo configuration.The remaining steps to produce citrinin from (-)-2 required carboxylation to 11, formylation and in situ ring closure with ethyl orthoformate to produce the required quinomethide structure.Application of the same reactions to (+/-)-9 and (+/-)-2 afforded (+/-)-citrinin in 40percent overall yield. - Key Words: Citrinin, (3R,4S)-(-)- / 2,3-Dimethyloxirane, trans-(-)- and cis- / Synthesis of erythro- and threo-3-arylbutan-2-ols
A Diastereoselective Synthesis of the Polyketide Antibiotic Citrinin using Toluate Anion Chemistry
Barber, Jill A.,Staunton, James,Wilkinson, Michael R.
, p. 2101 - 2110 (2007/10/02)
The diastereoselectivity of various synthetic approaches to (+/-)-threo-3-(3,5-dihydroxy-2-methylphenyl)butan-2-ol ('Phenol B') (4), based on reactions of benzyl anions with electrophiles, has been investigated.The anion (9) derived from ethyl 2,4-dimethoxy-6-ethylbenzoate reacted with acetaldehyde to give mainly an erythro-product isolated as the lactone (12); acetylation with acetyl chloride to give a ketone, followed by reduction, gave mainly the required threo-lactone (11).An alternative route was frustrated by decomposition of the benzyl anion derived from 3,4-dihydro-6,8-dimethoxy-3-methyl-1H-2-benzopyran-1-one (17).Reduction of the carbonyl group of the threo-lactone (11) to a methyl gave the dimethyl ether of 'Phenol B', which was converted into (+/-)-citrinin (1).
