Synthesis of Sulfur‐Hybridized Pyracylene and the Unexpected Phenyl Shift Mediated Rearrangement of Scholl Reaction

We present herein a strategy towards the straightforward synthesis of a novel sulfur‐hybridized pyracylene, tetraceno[5,6‐bc:11,12‐b'c']dithiophene (TDT) derivatives, via 2‐fold FeCl3‐mediated Scholl reaction. Surprisingly, the substituents on the precursors will guide the synthetic route, when the substituents were bromo‐ or phenyl‐, quantitatively debromination or phenyl ring shift mediated rearrangement were observed respectively, the rearrangement products were identified by the HR‐Mass and 2D NMR analyses. Additionally, a retrosynthetic method was adopted to confirm the unexpected reaction results in rearrangement of Scholl reaction. The synthesis of Sulfur‐hybridized pyracylenes (SHPs) was reported. Quantitatively debromination and phenyl ring‐shift‐mediated rearrangement induced by the substituents were observed. A retrosynthetic method was successfully adopted to confirm the unexpected reaction results in rearrangement of Scholl reaction.