Visible-Light-Induced Photoannulation of α-Naphthyl Cyclopropane Carboxylic Esters to Functionalized Dihydrophenalenes

A general synthetic entry to functionalized dihydrophenalenes has been found using naphthyl-cyclopropane esters as starting materials. The desired annulation was possible with visible light, Ir(Fppy)(3) as photocatalyst, BnNMe2 or DABCO as electron donor, HAT-catalyst, and proton source. A broad scope of substituted naphthyl and azanaphthyl derivatives provided the photoannulation products in high yield. Deuteration studies support a photoredox mechanism involving the photoreductive cyclopropane opening to an enolate radical followed by an aryl radical trapping.

Automated summary

A general synthetic method for functionalized dihydrophenalenes using naphthyl-cyclopropane esters as starting materials has been discovered. The reaction involves visible light, Ir(Fppy)(3) as photocatalyst, BnNMe2 or DABCO as electron donor, HAT-catalyst, and proton source to achieve high yields of photoannulation products. Deuteration studies suggest a photoredox mechanism with photoreductive cyclopropane opening to form an enolate radical and subsequent aryl radical trapping.