Modular synthesis of highly substituted benzenes from pericyclic cascade of divinyl carbinols

The synthesis of aromatic compounds is fundamental in chemistry, and the selective introduction of desired substituents onto aromatic rings remains a key research focus. Here, we report that highly substituted arenes can be synthesized in a single step from vinyl sulfoxide tethered divinyl carbinols through a cascade sequence involving Claisen rearrangement, sulfoxide elimination, 6π-electrocyclization, and auto-oxidation. Notably, variation in the reaction temperature allows for the isolation of a triene aldehyde intermediate. This method does not require the use of explosive reagents, rare transition metals, or an inert atmosphere. Acyclic divinyl carbinol precursors are readily accessible by the addition of relevant nucleophiles to unsaturated aldehydes, allowing modular installation of four different substituents. The substituent pattern of the carbinol is directly transferred to the arene, enabling access to previously challenging aromatic substitution motifs. The formation of an aldehyde functional group on the benzene ring is an added advantage. We demonstrated the utility of this approach in the first total synthesis of Nigerapyrone B, leveraging the aldehyde functionality.