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

Six new terpenes, including one harziane diterpene, 3R-hydroxy-9R,10R-dihydroharzianone (1), one proharziane diterpene, 11R-methoxy-5,9,13-proharzitrien-3-ol (2), three cyclonerane sesquiterpenes, 11-methoxy-9-cycloneren-3,7-diol (3), 10-cycloneren-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.