An unprecedented diacetoxyiodobenzene induced direct arylation of guaiacol derivatives and electron-rich arenes using a Lewis acid as an activator furnishes unsymmetrical biaryls without prefunctionalization of both coupling partners. The addition of electron-rich arenes on the α-position of electrophilic masked o-benzoquinones in an anti-Michael addition fashion affords the highly oxygenated unsymmetrical biaryls in good to excellent yields.