Synthesis of enantiopure planar chiral bis-(para)-pseudo-meta-type [2.2]paracyclophanes.

Abstract

A new type of planar chiral (Rp )- and (Sp )-4,7,12,15-tetrasubstituted [2.2]paracyclophanes was prepared from racemic 4,7,12,15-tetrabromo[2.2]paracyclophane as the starting substrate. Regioselective lithiation and transformations afforded racemic bis-(para)-pseudo-meta-type [2.2]paracyclophane (4,15-dibromo-7,12-dihydroxy[2.2]paracyclophane). Its optical resolution was performed by the diastereomer method using a chiral camphanoyl group as the chiral auxiliary. The diastereoisomers were readily isolated by simple silica gel column chromatography, and the successive hydrolysis afforded (Rp )- and (Sp )-bis-(para)-pseudo-meta-type [2.2]paracyclophanes ((Rp )- and (Sp )-4,15-dibromo-7,12-dihydroxy[2.2]paracyclophanes). They can be used as pseudo-meta-substituted chiral building blocks.