Minor Constituents fromPhyllostictasp. and Their Correlation with Epoxydon (Phyllosinol)

Metabolites of the higher fungi. Part 32. Rosnecatrone, a phytotoxic bicyclo[4.1.0]hept-3-en-2-one from the fungus Rosellinia necatrix Prill

“…In addition a configurational inversion will be expected at C-1. A naturally occurring mono-acetate from a Phylosticta species 19 shows similar structural features and…”

Effect of Chloride Ions on Anthrasesamone C Production in aSesamum indicumHairy Root Culture and Identification of the Precursor for Its Abiotic Formation

“…Nabeta et al 14,15) have reported similar non-enzymatic chlorination of the epoxy compound, epoxydon [5,6-epoxy-4-hydroxy-2-(hydroxymethyl)cyclohex-2-en-1-one], using a culture medium containing chloride ions. Epoxydon is biosynthesized from the hydroquinone, gentisyl alcohol [2-(hydroxymethyl)benzene-1,4-diol], by a fungus of Phyllosticta sp.…”

Arenicolins: C-Glycosylated Depsides from Penicillium arenicola

“…The relative configurations of the two stereogenic moieties in 1 could not be definitively correlated because of their distance from one another, but absolute configurations are proposed for them individually based on biogenetic precedents. The absolute configuration of the 2-hydroxymethyl-4,5,6-trihydroxy­cyclohexenone substructure is proposed as (16′ S , 17′ R , 18′ R ) based on its likely origin from the pathway leading to the known fungal metabolite epoxydon, as was judged to be the case for the structurally analogous fungal metabolites epoxydon 6-methylsalicylate ester, epoxydine B, epoxydon 3-chlorosalicylate ester, and 6 S -acetoxy-4 R ,5 R -dihydroxy-2-hydroxymethyl­cyclohex-2-en-1-one . The latter compound and epoxydine B differ from 1 by having much simpler acyl groups linked at the analogous position of the substituted cyclohexenone unit.…”

“…COSY and HMBC correlations allowed the straightforward assembly of the remaining subunit of the molecule as a 2-hydroxymethyl-4,5,6-trihydroxy­cyclohexenone unit. Coupling values for H-17′ with H-16′ ( J = 10.7 Hz) and H-18′ ( J = 3.9 Hz) and comparison with model compounds containing this unit indicated trans and cis relative orientations for the H16′–H17′ and H17′–H18′ relationships, respectively. − An HMBC correlation between H-16′ and carboxyl carbon C-1′ indicated that C-1′ was esterified to the C-16′ oxygen atom of this unit. Notably, H-16′ was the only oxymethine in the molecule with a significant downfield shift increment suggestive of acylation (δ H 5.94).…”