Photochemical 1,3-cycloaddition of olefins to aromatic compounds

One‐Step Synthesis of Benzotetra‐ and Benzopentacyclic Compounds through Intramolecular [2+3] Photocycloaddition of Alkenes to Naphthalene

“…[2] However, little is known about the [2+3] photocycloaddition of alkenes to naphthalene at the 1,3-positions, except the relatively inefficient intermolecular photocycloaddition of cyclooctene to naphthalene. [6] We now report a novel intramolecular [2+3] photocycloaddition of 1-cyano-2-(4-pentenyl)naphthalene derivatives to give benzotetra-and benzopentacyclic compounds with tri-and tetraquinane skeletons in a highly selective manner. [7,8] Irradiation of an acetonitrile solution containing 1 a (0.03 m) with a high-pressure mercury lamp through a Pyrex filter (> 280 nm) and under an argon atmosphere exclusively gave a benzotetracyclic product (3 a) in 70 % yield (Scheme 1).…”

The Double [3+2] Photocycloaddition Reaction

“…Wilzbach and Kaplan 19 of the Argonne National Laboratory, Illinois and Bryce-Smith, Gilbert and Orger 20 of Reading University. Both groups found that direct irradiation, using 253.7 nm UV light, of a solution containing an olefin (such as cyclooctene 28) and an aromatic compound like benzene (29), resulted in a 1:1 non-aromatic adduct that appeared to contain a vinyl cyclopropane unit at its core (Scheme 1.6).…”

Alkene–Arene meta Photocycloadditions with a Four‐Carbon‐Atom Tether: Efficient Approach toward the Polycyclic Ring Systems of Aphidicolin and Stemodinone

“…[1][2][3][4] Extensive experimental and theoretical investigations of this reaction over the ensuing 38 years have greatly advanced the understanding of its mechanism and synthetic potential, [3][4][5] although much remains to be addressed. In 1969, Morrison and Ferree reported the first example of the intramolecular variant of this reaction.…”