Modular α-Functionalization of Bowl-Shaped Subphthalocyanine Aromatics.

Herein a general strategy for the α-functionalization of subphthalocyanines (SubPcs) via palladium-catalyzed cross-coupling reactions is described. Despite the higher steric demand of α-SubPcs, C3-symmetric iodinated precursors were found to readily undergo α-arylation, alkynylation, alkenylation, and C-N coupling. This strategy is also applicable to enantiopure and even more sterically congested (C1-symmetric) tri- and hexa-substituted derivatives. Thus, these results open the door to a previously inaccessible regioisomeric target for the design of functional nonplanar aromatics.