Manipulating carbon-centered radicals to add to electron-deficient systems is a well-precedented process. By coupling the Fe(II)-mediated Fenton reaction with the Fe(III)-mediated single-electron oxidation of anisolic compounds, we demonstrate how electron-rich carbon-centered radicals can react with electron-rich arenes through a radical-polar cascade pathway. This bioinspired approach produces diarylmethane derivatives from simple unfunctionalized precursors.