Structure And Absolute Configuration Of Pseudohygrophorones A(12) And B-12, Alkyl Cyclohexenone Derivatives From Hygrophorus Abieticola (Basidiomycetes)

Pseudohygrophorones A(12) (1) and B-12 (2), the first naturally occurring alkyl cyclohexenones from a fungal source, and the recently reported hygrophorone B-12 (3) have been isolated from fruiting bodies of the basidiomycete Hygrophorus abieticola Krieglst. ex Groger & Bresinsky. Their structures were assigned on the basis of extensive one- and two-dimensional NMR spectroscopic analysis as well as ESI-HRMS measurements. The absolute configuration of the three stereogenic centers in the diastereomeric compounds 1 and 2 was established with the aid of (3)J(H,H) and (4)J(H,H) coupling constants, NOE interactions, and conformational analysis in conjunction with quantum chemical CD calculations. It was concluded that pseudohygrophorone A(12) (1) is 4S,5S,6S configured, while pseudohygrophorone B-12 (2) was identified as the C-6 epimer of 1, corresponding to the absolute configuration 4S,5S,6R. In addition, the mass spectrometric fragmentation behavior of 1-3 obtained by the higher energy collisional dissociation method allows a clear distinction between the pseudohygrophorones (1 and 2) and hygrophorone B-12 (3). The isolated compounds 1-3 exhibited pronounced activity against phytopathogenic organisms.