2-Methoxy-1, 4-benzoquinone can be alkylated selectively with trialkylboranes in position 5, givinghigh yields of 5-alkyl-2-methoxy-1, 4-benzoquinones after oxidative work up. In the case of 2-hydroxy-1, 4-naphthoquinone, the same procedure leads to 3-alkylated products. A radical chain mechanism is proposed to explain the observed selectivity.