Controllable 1,4-Palladium Aryl to Aryl Migration in Fused Systems─Application to the Synthesis of Azaborole Multihelicenes.

Abstract

Herein, we report the first 1,4-Pd aryl to aryl migration/Miyaura borylation tandem reaction in fused systems. The Pd shift occurred in the bay region of the dibenzo[g,p]chrysene building blocks, giving rise to a thermodynamically controlled mixture of 1,8- and 1,9-borylated compounds that allowed the preparation of regioisomeric azaborole multihelicenes from the same starting material. The outcome of this synthesis can be controlled by the choice of reaction conditions, allowing the migration process to be turned off in the absence of an acetate additive and the target multiheterohelicenes to be prepared in a regioselective manner. The target compounds show bright green fluorescence in dichloromethane with emission quantum yields (Φ) of up to 0.29, |g_lum| values up to 2.7 × 10^-3, and green or green-yellow emission in the solid state, reaching Φ of 0.22. Single crystal X-ray diffraction analyses gave insight into their molecular structures and the packing arrangement. Evaluation of aromaticity in these multihelicenes revealed a nonaromatic character of the 2H-1,2-azaborole constituent rings.