Bowl-Shaped Symmetric and Non-symmetric Bis-functionalized Indacenopicenes

Regioselective arrangement of two groups of orthogonal reactivity in bowl-shapedas-indaceno[3,2,1,8,7,6-pqrstuv]picene(Idpc) was key for the synthesis of hetero-bis-functionalized Idpcderivatives. Halogen and methyl groups were positioned at specificpositions in the rim area of Idpc at an early stage during the synthesisby functionalization of suitable precursors. Regioselective function-alization of the bowl's rim was thenfinally achieved either viaconsecutive Cu(I)-catalyzed azide-alkyne coupling (CuAAC) andC-C cross-coupling reactions or by C-C cross-coupling alone,giving access to either symmetric or non-symmetric bis-functionalizedIdpc derivatives. The self-aggregation behavior of9cin solution wasinvestigated by recording a series of concentration-dependent NMRspectra. The aggregation constant of9cwas determined by anonlinear least-squares treatment of the1H NMR shift data to be 2.9 +/- 0.2 M-1, and the formation of dimers was found to be the prevailing process

Automated summary

The regioselective functionalization of the bowl-shaped Idpc is crucial for the synthesis of hetero-bis-functionalized Idpc derivatives. By positioning halogen and methyl groups at specific positions in the rim area of Idpc, either through consecutive CuAAC and C-C cross-coupling reactions or by C-C cross-coupling alone, symmetric or non-symmetric bis-functionalized Idpc derivatives can be obtained.