C─S Bond Formation of Aryl Germanes.

Aryl germanes have emerged as robust and orthogonal coupling partners, but the chemistry enabling their functionalization is still in its infancy. Herein, we report the first C─S bond formation of aryl germanes. In contrast to conventional C─S cross-couplings of prefunctionalized arenes that largely rely on transition-metal catalysis, this transformation proceeds in the absence of a metal catalyst at room temperature and tolerates air and moisture. The reaction is orthogonal to common coupling handles, including aryl halides and aryl silanes, enabling selective thiolations in multifunctional molecules. Mechanistic studies support a radical-based aromatic substitution pathway.