Unprecedented pseudo-ortho and ortho metallation of [2.2]paracyclophanes – a methyl group matters

The first example of a pseudo-ortho metallation on [2.2]paracyclophane is presented, giving easy access to enantiopure compounds of this type. By slight modification of the directing group, metallation of the ortho- and C2-positions is possible. The mechanism was further investigated by means of density functional theory (DFT) calculations.