Molecular Iodine-Mediated One-Pot Sequential Iodocyclization–Decarboxylative Protodeiodination: Access to Densely Functionalized Benzofulvenes

A stereoselective, metal-free synthesis of densely functionalized benzofulvenes <i>via</i> base-promoted regioselective iodocyclization followed by decarboxylative protodeiodination of <i>o</i>-alkynylaryl 2-cyanoacrylates is described. Michael addition of alcohol to the carbon-carbon double bond triggers the sequential formation of the C-O, C-C, and C-I bonds in a single operation. Subsequent decarboxylation and the elimination of HI furnish the final benzofulvene framework, featuring an exocyclic double bond and functional groups such as -CN and -OMe that can be easily transformed to afford biologically active pharmacophores.