Allium Species from Central and Southwest Asia Are Rich Sources of Marasmin

Marasmin, which is especially known from the two South African species Tulbaghia alliacea and Tulbaghia violacea, but was also described for the garlic mushroom Marasmius alliaceus, is the precursor of the thiosulfinate marasmicin. Marasmicin has attracted considerable attention because of its antifungal and tuberculostatic activities. However, many Allium species of the subgenus Melanocrommyum, especially Allium suworowii, are also very rich in marasmin. A. suworowii revealed concentrations of marasmin up to 1.6%, related to the fresh weight of bulbs, and up to 3.0%, related to air-dried fruiting bodies, of the corresponding γ-glutamylmarsmin was found in M. alliaceus. Both species show much higher amounts of marasmin as Tulbaghia and could be considered as natural sources for the isolation of this compound. Further promising Allium species with considerable amounts of marasmin besides other cysteine sulfoxides are Allium stipitatum and Allium altissimum. (R S ,R C )-Marasmin is typical for the investigated species of the subgenus Melanocrommyum, whereas γ-glutamyl-(S S ,R C )-marasmin is the only cysteine sulfoxide for the genus Marasmius known until now. Both cysteine sulfoxides were isolated and described as o-phthaldialdehyde (OPA) derivatives. Furthermore, the cysteine sulfoxides methiin, propiin, S-(2-pyrrolyl)-cysteine sulfoxide, eventually S-(2-pyridyl)-cysteine sulfoxide and S-(2-pyridyl)-L-cysteine N-oxide were found.