A bioactive disubstituted nonenolide, named truncatenolide,
was
produced by Colletotrichum truncatum, which was collected from infected tissues of soybean showing anthracnose
symptoms in Argentina. This is a devastating disease that drastically
reduces the yield of soybean production in the world. The fungus also
produced a new trisubstituted oct-2-en-4-one, named truncatenone,
and the well-known tyrosol and N-acetyltyramine.
Truncatenolide and truncatenone were characterized by spectroscopic
(essentially one-dimensional (1D) and two-dimensional (2D) 1H and 13C NMR and HR ESIMS) and chemical methods as (5E,7R,10R)-7-hydroxy-10-methyl-3,4,7,8,9,10-hexahydro-2H-oxecin-2-one and (Z)-6-hydroxy-3,5-dimethyloct-2-en-4-one,
respectively. The geometry of the double bond of truncatenolide was
assigned by the value of olefinic proton coupling constant and that
of truncatenone by the correlation observed in the corresponding NOESY
spectrum. The relative configuration of each stereogenic center was
assigned with the help of 13C chemical shift and 1H–1H scalar coupling DFT calculations, while the
absolute configuration assignment of truncatenolide was performed
by electronic circular dichroism (ECD). When tested on soybean seeds,
truncatenolide showed the strongest phytotoxic activity. Tyrosol and N-acetyltyramine also showed phytotoxicity to a lesser extent,
while truncatenone weakly stimulated the growth of the seed root in
comparison to the control. When assayed against Macrophomina
phaseolina and Cercospora nicotianae, other severe pathogens of soybean, truncatenolide showed significant
activity against M. phaseolina and
total inhibition of C. nicotianae.
Thus, some other fungal nonenolides and their derivatives were assayed
for their antifungal activity against both fungi in comparison with
truncatenolide. Pinolidoxin showed to a less extent antifungal activity
against both fungi, while modiolide A selectively and totally inhibited
only the growth of C. nicotianae. The
SAR results and the potential of truncatenolide, modiolide A, and
pinolidoxin as biofungicides were also discussed.