Diastereoselective Hartwig-Buchwald reaction of chiral amines with rac-[2.2]paracyclophane derivatives

A Hartwig-Buchwald addition of a variety of chiral amines to rac-4-bromo-2.2]paracyclophane and rac-trifluoromethanesulfonic acid (4-2.2]paracyclophane) ester was performed with high diastereoselectivities. Kinetic racemic resolution of the starting materials was achieved, providing a rapid access to enantiomerically enriched 4-bromo-2.2]paracyclophane and the corresponding enantiomerically pure 2.2]paracyclophane amines. Additionally, the first reaction of a secondary amine with a 2.2]paracyclophane halide was achieved.