Synthesis of Phenanthridin-6(5H)-ones via Copper-Catalyzed Cyclization of 2-Phenylbenzamides

Abstract

Synthesis of phenanthridin-6(5H)-ones was achieved via copper-catalyzed cyclization of 2-phenylbenzamides using air as the oxidant and KOt-Bu as the base. It was discovered that, besides Ph₃P, other ligands such as 1,10-phenanthroline, TMEDA as well as l-proline could also be used as the ligand to effect the transformation.

Key words

phenanthridin-6(5H)-ones - Cu-catalyzed - cyclization - 2-phenylbenzamides - air

• References and Notes

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• 20 To a stirred solution of CuI (8.6 mg, 0.05 mmol) and Ph₃P (26.2 mg, 0.10 mmol) in anhyd o-xylene (3.0 mL) were added 2-phenylbenzamide (1; 99 mg, 0.5 mmol) and KOt-Bu (112 mg, 1.0 mmol) at r.t. A balloon of air was attached to the system and the mixture was heated at 120 °C for 18 h. After cooling to r.t., the reaction mixture was diluted with Et₂O (25 mL) and H₂O (25 mL). The aqueous layer was extracted with Et₂O (3 × 25 mL). The organic layers were combined, dried with MgSO₄, filtered, and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel (petroleum ether–EtOAc) to afford the desired product (87.8 mg) in 90% yield.