A Catalytic SEAr Approach to Dibenzosiloles Functionalized at Both Benzene Cores

A general procedure for the catalytic preparation of dibenzosiloles functionalized at one or both benzene rings starting from readily available ortho-silylated biphenyls is reported. This method provides rapid access to silole building blocks substituted with chlorine atoms at both phenylene groups, thereby allowing catalytic access to directly polymerizable dibenzosiloles. Moreover, it is shown that, despite the involvement of highly electrophilic intermediates, a considerable range of Lewis-basic, for example, oxygen- and nitrogen-containing, functional groups is tolerated. The mechanism of this intramolecular electrophilic aromatic substitution (SE Ar) proceeds through a sulfur-stabilized silicon cation, generated catalytically from the hydrosilane precursor.