The synthesis of optically active piperidines by enantioselective addition of aryl Grignard reagents to pyridine N-oxides and lithium binolate followed by reduction is reported for the first time. The reaction results in high yields (51鈥?4%) in combination with good ee (54鈥?0%). Some of these products were subsequently recrystallized, affording enhanced optical purities (>99% ee).