9-Silafluorenes via Base-Promoted Homolytic Aromatic Substitution (BHAS) - The Electron as a Catalyst

Transition-metal-free intramolecular radical silylation of 2-diphenylsilylbiaryls via base-promoted homolytic aromatic substitution (BHAS) to give 9-silafluorenes is reported. 2-Diphenylsilylbiaryls are readily prepared, and cross dehydrogenative silylation occurs with tert-butylhydroperoxide (TBHP) as a cheap stoichiometric oxidant in the presence of a small amount of tetrabutylammonium iodide (TBAI) as an initiator. These cyclizations are catalyzed by the electron.