Abstract: | In a single photochemical operation (λ≥350 nm) an easily accessible indanone derivative was converted into a structurally complex precursor of the protoilludane sesquiterpenes. The product (60 % yield) contains all 15 carbon atoms of the skeleton in the required connectivity and was transformed into the natural product atlanticone C (9 steps, 6 % overall yield). In addition, it was shown that other protoilludanes, such as Δ6‐protoilludene and paesslerin A, can be prepared in a concise fashion via the photochemical key intermediate. The photochemical reaction cascade comprises an ortho photocycloaddition, a thermal disrotatory ring opening and a regioselective disrotatory 4π] photocyclization. |