A New Harziane Diterpene,Harziaketal A,and a New Sterol,Trichosterol A,from the Marine-Alga-Epiphytic Trichoderma sp. Z43

One new diterpene, harziaketal A ( 1 ), and one new highly degraded sterol, trichosterol A ( 2 ), along with three known compounds, including one diterpene, harzianone ( 3 ), and two steroids, (22E,24R)-5α,6α-epoxy-ergosta-8(14),22-dien-3β,7α-diol ( 4 ) and isoergokonin B ( 5 ), were isolated from the culture of the marine-alga-epiphytic fungus Trichoderma sp. Z43 by silica gel column chromatography (CC), Sephadex LH-20 CC, and preparative thin-layer chromatography (TLC). Their structures and relative configurations were assigned by nuclear magnetic resonance (NMR) and high resolution electrospray ionisation mass spectrometry (HR-ESI-MS) data, and the absolute configuration of 1 was established by X-ray diffraction. Compound 1 features a hemiketal unit situated at the four-membered ring of harziane-type diterpenes for the first time, while 2 represents the rare occurrence of sterols with rings A and B being degraded. Compounds 1 and 2 displayed weak inhibition against the tested phytoplankton (Amphidinium carterae, Heterocapsa circularisquama, Heterosigma akashiwo, and Prorocentrum donghaiense) with half maximal inhibitory concentration (IC₅₀) ranging from 14 to 53 μg/mL.