Synthesis of cis/trans-dihydrochromenones via a photoinduced rearrangement of 4-phenyl-3-aryl/cyclohexenylcoumarins

A concise and environmentally friendly protocol has been developed for the synthesis of cis-dihydrochromenones and trans-dihydrochromenones in EtOH at room temperature. Irradiation of 4-phenyl-3-arylcoumarins in EtOH with 313 nm UV light under an argon atmosphere at room temperature gave cis-4b,15c-dihydro-16H-benzofuro[3 ',2 ':7,8]phenanthro[9,10-c]chromen-16-ones and cis-8c,14b-dihydro-9H-benzo[11,12]chryseno[5,6-c]chromen-9-ones in good yields. And an analogous treatment of 4-phenyl-3-alkenylcoumarins as 4-phenyl-3-arylcoumarins provided trans-1,2,3,4,4a,14b-hexahydro-5H-phenanthro[9,10-c]chromen-5-ones. The described photorearrangement proceeded smoothly without the addition of any transition metals and additives. The photorearrangement of 4-phenyl-3-arylcoumarins is believed to proceed via 6 pi-electrocyclization, a [1,3]-hydrogen shift and keto-enol isomerization.

Automated summary

A concise and environmentally friendly protocol has been developed for the synthesis of cis-dihydrochromenones and trans-dihydrochromenones in EtOH at room temperature. The described photorearrangement proceeded smoothly without the addition of any transition metals and additives, providing good yields. It is believed that the photorearrangement of 4-phenyl-3-arylcoumarins proceeds via 6 pi-electrocyclization, a [1,3]-hydrogen shift and keto-enol isomerization.