Diterpenes and Sesquiterpenes from the Marine Algicolous Fungus Trichoderma harzianum X-5

Abstract

Six new terpenes, including one harziane diterpene, 3R-hydroxy-9R,10Rdihydroharzianone (1), one proharziane diterpene, 11R-methoxy-5,9,13-proharzitrien-3-ol (2), three cyclonerane sesquiterpenes, 11-methoxy-9-cycloneren-3,7-diol (3), 10cycloneren-3,5,7-triol (4), and methyl 3,7-dihydroxy-15-cycloneranate (5), and one acorane sesquiterpene, 8-acoren-3,11-diol (6), were isolated from the culture of Trichoderma harzianum X-5, an endophytic fungus obtained from the marine brown alga Laminaria japonica. Their structures and relative configurations were established by analysis of 1D/2D NMR, HREIMS, and IR data, and the absolute configurations were assigned on the basis of ECD curves or biogenetic considerations. These terpenes possess four different carbon skeletons, and compound 2, with a rarely occurring bicyclic framework, represents a possible precursor of tetracyclic harzianes. Compounds 1−6 exhibited growth inhibition of some marine phytoplankton species.

Terpenoids From the Coral-Derived Fungus Trichoderma harzianum (XS-20090075) Induced by Chemical Epigenetic Manipulation

“…Compared to the rice culture control at the same culture condition, the HPLC finger-print of the EtOAc extract of the culture with sodium butyrate (10 µM) in rice medium showed new peaks at about 15, 31, and 38 min ( Figure 1A), and the main peaks of the harziane diterpenoids at 33-42 min ( Figure 1B) disappeared. Chemical investigation of the EtOAc extract led to the isolation of three new terpenoids, including one novel chlorinated cleistanthane diterpenoid, harzianolic acid A (1), one harziane diterpenoid, harzianone E (2), and one cyclonerane sesquiterpenoid, 3,7,11-trihydroxy-cycloneran (3), together with 11 known sesquiterpenoids, including eight cyclonerane sesquiterpenoids, methyl 3,7-dihydroxy-15cycloneranate (4) (Song et al, 2018), catenioblin C (5) (Wu et al, 2012), ascotrichic acid (6) (Xie et al, 2013), cyclonerotriol (7) (Kasitu et al, 1992), (10E)-12-acetoxy-10-cycloneren-3,7-diol (8) (Fang et al, 2018), cyclonerodiol (9) (Nozoe et al, 1970), cyclonerodiol oxide (10) (Fujita et al, 1984) and epicyclonerodiol oxide (11) (Fujita et al, 1984), one african sesquiterpenoid, ophioceric acid (12) (Reátegui et al, 2005), and two acoranetype sesqiuterpenoids, ent-trichoacorenol (13) (Brock and Dickschat, 2011) and trichoacorenol (14) (Huang et al, 1995) (Figure 2). These results revealed that the original main products harziane diterpenoids were replaced by cyclonerane sesquiterpenoids.…”

“…Mosher's method (Cao et al, 2014) was tried to determine the absolute configuration of C-7 but failed. Fortunately, a literature survey revealed that the coisolated cyclonerane-type compounds (4-9) and many other similar natural compounds have been reported the same absolute configurations as 2S,3R,6R,7R (Hanson et al, 1975;Kasitu et al, 1992;Li et al, 2007;Wu et al, 2012;Xie et al, 2013;Zhang et al, 2017;Fang et al, 2018;Song et al, 2018). Therefore, based on the biogenetic considerations, compound 3 was proposed to have the same absolute configuration (2S,3R,6R,7R) as the co-isolated compound 9, which was also supported by their similar OR between 3 ([α] 22 D -29.9 (c 1.00, CHCl 3 )) and 9 ([α] 22 D -26.6 (c 1.00, CHCl 3 ); lit.…”

“…Compounds 4-14 were identified to be methyl 3,7-dihydroxy-15-cycloneranate (Song et al, 2018), catenioblin C (Wu et al, 2012), ascotrichic acid (Xie et al, 2013), cyclonerotriol (Kasitu et al, 1992), (10E)-12-acetoxy-10-cycloneren-3,7-diol (Fang et al, 2018), cyclonerodiol (Nozoe et al, 1970), cyclonerodiol oxide (Fujita et al, 1984), epicyclonerodiol oxide (Fujita et al, 1984), ophioceric acid (Reátegui et al, 2005), ent-trichoacorenol (Brock and Dickschat, 2011), and trichoacorenol (Huang et al, 1995), respectively, by comparing their NMR data with those in the literature. The absolute configuration of 12 (1R,2S,4S) was confirmed for the first time using the method of single X-ray diffraction with the Flack's parameter of −0.05(5) (Figure 5).…”

Metabolites from marine invertebrates and their symbiotic microorganisms: molecular diversity discovery, mining, and application

“…Terpenoids constitute a class of broadly active natural products isolated from a diverse range of marine organisms. For example, 11R-methoxy-5,9,13-proharzitrien3-ol, obtained from an endophytic fungus Trichoderma harzianum X-5 derived from the marine brown alga Laminaria japonica, displayed growth inhibition of some marine phytoplankton species (Song et al 2018). Nakijinol G, a meroterpenoid obtained from a sponge Hyrtios sp.…”

Sesquiterpenes and Cyclodepsipeptides from Marine-Derived Fungus Trichoderma longibrachiatum and Their Antagonistic Activities against Soil-Borne Pathogens

“…T. longibrachiatum is generally isolated from terrestrial soil and plants [11][12][13][14], being a rare marine resource [15]. Ji and co-workers isolated various Trichoderma species from marine alga which could produce structurally unique and biologically active metabolites [16][17][18][19], also indicating the research potential of marine-derived Trichoderma species.…”