Modular Approach to the Synthesis of Two-Dimensional Angular Fused Acenes

Herein, we present a modular approach to pristine angularly fused planar acenes. The approach includes the Pd-catalyzed fusion of several building blocks and implements a dehydrative π-extension (DPEX) reaction as a key step enabling facile access to diverse two-dimensional acenes. The scope was demonstrated on nine examples with up to quantitative yield.