New Pulvinic Acid and Phenylalaninol Derivatives from the Mushrooms Retiboletus griseus and R. nigerrimus

The close genetic relationship of the mushrooms Retiboletus griseus and R. nigerrimus is supported by the occurrence of the orange-yellow retiboletic acid, resp. its methyl ester, in both species. The structures of these highly substituted pulvinic acid derivatives have been elucidated by spectroscopic investigations. R. nigerrimus also contains two N-protocatechuyl-L-phenylalaninol derivatives, nigerrimin A and B, the first reported occurrence of such compounds in nature. Their configuration was established by the synthesis of nigerrimin B.