Biotransformation of labdane and halimane diterpenoids by two filamentous fungi strains

Biotransformation of natural products by filamentous fungi is a powerful and effective approach to achieve derivatives with valuable new chemical and biological properties. Although diterpenoid substrates usually exhibit good susceptibility towards fungi enzymes, there have been no studies concerning the microbiological transformation of halimane-type diterpenoids up to now. In this work, we investigated the capability of Fusarium oxysporum (a fungus isolated from the rhizosphere of Senna spectabilis ) and Myrothecium verrucaria (an endophyte) to transform halimane ( 1 ) and labdane ( 2 ) acids isolated from Hymenaea stigonocarpa (Fabaceae). Feeding experiments resulted in the production of six derivatives, including hydroxy, oxo, formyl and carboxy analogues. Incubation of 1 with F. oxysporum afforded 2-oxo-derivative ( 3 ), while bioconversion with M. verrucaria provided 18,19-dihydroxy ( 4 ), 18-formyl ( 5 ) and 18-carboxy ( 6 ) bioproducts. Transformation of substrate 2 mediated by F. oxysporum produced a 7 α -hydroxy ( 7 ) derivative, while M. verrucaria yielded 7 α - ( 7 ) and 3 β -hydroxy ( 8 ) metabolites. Unlike F. oxysporum , which showed a preference to transform ring B, M. verrucaria exhibited the ability to hydroxylate both rings A and B from substrate 2 . Additionally, compounds 1 – 8 were evaluated for inhibitory activity against Hr-AChE and Hu-BChE enzymes through ICER-IT-MS/MS assay.

Exploiting a Step in Diterpenoid Biosynthesis by the Fungus Fusarium Fujikuroi

The scope of the microbiological transformation of ent-kaurenoid diterpenes by the fungus Fusarium (Gibberella) fujikuroi which utilise the ent-kaurene and ent-kauren-19-oic acid oxidases and the ring contraction of ring B to gibberellin is reviewed. Constraints arising from the presence of 3α, 15α and 18-hydroxyl groups are noted. The development of a group of potential plant growth regulators which inhibit the ring contraction step in gibberellin biosynthesis is described.