DMAP-[2.2]paracyclophane: Observation of an Unusual C-C Insertion

A novel family of nucleophilic catalysts derived from 4-(dimethylamino)pyridine (DMAP) is described. The aminopyridine moiety is attached to a [2.2]paracyclophane skeleton, giving a catalyst with intrinsic planar chirality. Their synthesis is described starting from aminoparacyclophane 5 in four steps. In the course of this preparation, an unprecedented rearrangement involving a C-C bond insertion was observed, leading to an unexpected quinolone-phenyl[2.2]cyclophane (8). The target catalyst 16 was obtained in enantiopure form by formation of diastereomers with a chiral secondary amine, allowing simple chromatographic separation. Preliminary catalytic studies were also performed.