Discovery of Cadinane-Type Sesquiterpenoids from the Infected Stems of Hibiscus tiliaceus as Potential Agrochemical Fungicides.

Abstract

Ten new cadinane-type sesquiterpenoids, named hibisceusins I-R (1-10), along with 14 known sesquiterpenoids (11-24), were acquired from the tainted stems of Hibiscus tiliaceus. Their structures were identified via spectroscopic analysis, one-dimensional (1D) and two-dimensional (2D) NMR, and computer-assisted structure elucidation techniques, including infrared (IR) and mass spectrometry (MS) data. Additionally, subsequent DP4/DP4+ probability methods were used to resolve 3's relative configurations by comparing their experimental values to the predicted NMR data. The absolute configurations of compounds 1-4 were measured through electronic circular dichroism (ECD) spectra. The ability of all isolates to inhibit the growth of five phytopathogenic fungi (Rhizopus stolonifer, Verticillium dahliae Kleb., Thanatephorus cucumeris, Fusarium oxysporum Schltdl., and F. oxysporum HK-27) was evaluated. Aldehydated sesquiterpenoids (1, 6-9, 11, 12, and 22) and a known sesquiterpenoid quinine (18) exhibited significant inhibitory activities against V. dahliae, T. cucumeris, F. oxysporum, and F. oxysporum HK-27 with minimum inhibitory concentration (MIC) values of 2.5-50 μg/mL, but all isolates remained inactive against R. stolonifer. Moreover, the effects of the isolates on the mycelial morphology were watched through scanning electron microscopy. This study revealed that aldehydated cadinane-type sesquiterpenoids could be used as novel antifungal molecules to develop agrochemical fungicides in plant protection.