Toward a Formyl-to-Phenyl Conversion: An Unexpected Photochemical Fulvene Rearrangement

Abstract

Toward a conversion of aldehydes into arenes, we designed a sequence involving the initial reaction of an aldehyde to give a fulvene, followed by photochemical and platinum-catalyzed rearrangements into a Dewar benzene derivative, which finally isomerizes into the targeted arene. While computational studies support the plausibility of this route, we found that fulvene irradiation resulted in an unexpected isomerization into a spiro[2.4]heptadiene. This unusual photorearrangement has been investigated mechanistically and provides access to a variety of spiro[2.4]heptadienes with different substituents.

Keywords: Cyclopropanes; Fulvenes; Photochemistry; Rearrangement; Spiro-Compounds.