Radical Tandem Bicyclization Triggered by the α-Position of α,β-Unsaturated Ketones Bearing Nonterminal 1,6-Enynes: Synthesis of the 5H-Benzo[a]fluoren-5-one Skeleton.

A novel method for the synthesis of 5H-benzo[a]fluoren-5-one from inactive nonterminal 1,6-alkynes through a free radical tandem bicyclization process has been established. This process achieved a continuous cyclization triggered rarely by the α-position of α,β-unsaturated ketones. The reaction constructed three C-C bonds in one step with the readily accessible substrates and excellent substrate compatibility.