Lithiation of a series of cyclic aralkyl tertiary amines with sec-BuLi in various solvents has been studied. There is a subtle sensitivity to steric factors and lithium coordinating solvents/additives have an adverse effect. ortho-Lithiation is observed only in the case of an eight-membered cyclic amine and the ease of benzylic lithiation with respect to nitrogen is in the surprising order γ> β≫ α, δ. These observations are discussed in the context of ...