Transition-Metal-Free, Formal C-H Germylation of Arenes and Styrenes via Dibenzothiophenium Salts.

We report an operationally simple, selective, and transition-metal-free germylation of arenes and styrenes at room temperature, using a robust and bench-stable Ge source (R3Ge-SiR3) and dibenzothiophenium salts as enabling intermediates. The first direct engagement in cross-coupling of the newly made E-alkenyl germanes is also presented, allowing the chemoselective arylation under air-tolerant nanoparticle catalysis.