Efficient and selective: Frustrated Lewis pairs based on BF3⋅OEt2 and LiCl‐complexed tmpMg or tmpZn amides (tmp=2,2,6,6‐tetramethylpiperidyl) allow the efficient and regioselective metalation of various functionalized N heterocycles (see scheme for examples). Moreover, such metalations carried out in the presence or absence of BF3⋅OEt2 enable a complete switch of regioselectivity, thus allowing complementary functionalization.