<jats:title>Abstract</jats:title><jats:p>Two new amides derived from cinnamic acid, namely,(<jats:italic>R</jats:italic>)‐2‐hydroxyputrescine dicinnamamide (<jats:bold>4</jats:bold>) and pholiotic acid {(2<jats:italic>R</jats:italic>)‐2‐[(<jats:italic>S</jats:italic>)‐3‐hydroxy‐3‐methylglutaryloxy]putrescine dicinnamamide} (<jats:bold>5</jats:bold>), in addition to the known compound maytenine (<jats:italic>N</jats:italic><jats:sup>1</jats:sup>,<jats:italic>N</jats:italic><jats:sup>8</jats:sup>‐dicinnamoyl spermidine) (<jats:bold>3</jats:bold>) were isolated from the fruiting bodies of the Basidiomycete <jats:italic>Pholiota spumosa</jats:italic>. The absolute configuration of <jats:bold>4</jats:bold> was established as (<jats:italic>R</jats:italic>) by its total synthesis starting from (<jats:italic>S</jats:italic>)‐dimethylmalate, whereas that of <jats:bold>5</jats:bold> was determined by conversion into the known compound methyl (<jats:italic>S</jats:italic>)‐4‐[(<jats:italic>S</jats:italic>)‐1‐(1‐naphthalen‐1‐yl)ethylcarbamoyl]‐3‐hydroxy‐3‐methylbutanoate (<jats:bold>14</jats:bold>). Compounds <jats:bold>3</jats:bold> and <jats:bold>5</jats:bold> exhibited an inhibitory effect on cell growth of the androgen‐insensitive DU‐145 prostate cancer cells, which suggests that these fungal polyamine conjugates, like other polyamine analogues, might have chemotherapeutic potential against androgen‐independent prostatic cancer. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)