Intramolecular ortho Photocycloaddition of 4‑Substituted 7‑(4′-Alkenyloxy)-1-indanones and Ensuing Reaction Cascades

4-Substituted 7-(4′-alkenyloxy)-1-indanones were prepared from the respective substituted aryl propanoic acids and subjected to UV-A irradiation (λ = 350 or 366 nm). While the 4-chloro compound was directly converted at λ = 366 nm into a pentacyclic product (47% yield) by a three-photon cascade process, the oxygenated substrates reacted in trifluoroethanol at λ = 350 nm by a two-photon cascade, involving an ortho photocycloaddition, a thermal disrotatory ring opening, and a [4π] photocyclization (six examples, 67–82% yield). An ensuing photochemical di-π-methane rearrangement of the latter products was achieved by irradiation at λ = 350 nm in toluene (five examples, 36–70% yield). The diastereoselectivity of the reaction was probed employing a chiral 1-indanone with a stereogenic center at carbon atom C3. 1-Indanones with a 4-hexenyloxy side chain [(E)- or (Z)-configured] at carbon atom C7 served to interrogate the stereospecifity of the reaction.