Gulypyrones
A and B and Phomentrioloxins B and C Produced by <i>Diaporthe gulyae</i>, a Potential Mycoherbicide for Saffron Thistle (<i>Carthamus
lanatus</i>)
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Abstract
A virulent strain of <i>Diaporthe
gulyae</i>, isolated
from stem cankers of sunflower and known to be pathogenic to saffron
thistle, has been shown to produce both known and previously undescribed
metabolites when grown in either static liquid culture or a bioreactor.
Together with phomentrioloxin, a phytotoxic geranylcyclohexenetriol
recently isolated from a strain of <i>Phomopsis</i> sp.,
two new phytotoxic trisubstituted α-pyrones, named gulypyrones
A and B (<b>1</b> and <b>2</b>), and two new 1,<i>O</i>- and 2,<i>O</i>-dehydro derivatives of phomentrioloxin,
named phomentrioloxins B and C (<b>3</b> and <b>4</b>),
were isolated from the liquid culture filtrates of <i>D. gulyae</i>. These four metabolites were characterized as 6-[(2<i>S</i>)2-hydroxy-1-methylpropyl]-4-methoxy-5-methylpyran-2-one (<b>1</b>), 6-[(1<i>E</i>)-3-hydroxy-1-methylpropenyl]-4-methoxy-3-methylpyran-2-one
(<b>2</b>), 4,6-dihydroxy-5-methoxy-2-(7-methyl-3-methyleneoct-6-en-1-ynyl)cyclohex-2-enone
(<b>3</b>), and 2,5-dihydroxy-6-methoxy-3-(7-methyl-3-methyleneoct-6-en-1-ynyl)cyclohex-3-enone
(<b>4</b>) using spectroscopic and chemical methods. The absolute
configuration of the hydroxylated secondary carbon of the 2-hydroxy-1-methylpropyl
side chain at C-6 of gulypyrone A was determined as <i>S</i> by applying a modified Mosher’s method. Other well-known
metabolites were also isolated including 3-nitropropionic, succinic,
and <i>p</i>-hydroxy- and <i>p</i>-methylbenzoic
acids, <i>p</i>-hydroxybenzaldehyde, and nectriapyrone.
When assayed using a 5 mM concentration on punctured leaf disks of
weedy and crop plants, apart from 3-nitropropionic acid (the main
metabolite responsible for the strong phytotoxicity of the culture
filtrate), phomentrioloxin B caused small, but clear, necrotic spots
on a number of plant species, whereas gulypyrone A caused leaf necrosis
on <i>Helianthus annuus</i> plantlets. All other compounds
were weakly active or inactive