Germylation of Arenes via Pd(I) Dimer Enabled Sulfonium Salt Functionalization

Abstract

While aryl germanes have recently found usage as coupling partners in powerful catalytic applications, the synthetic access to this promising functionality is currently limited. This report details the straightforward synthesis of functionalized aryl triethylgermanes via formal C-H functionalization. Building on the concept of directing-group-free and site-selective C-H functionalization of arenes to thianthrenium salt intermediates, we showcase their efficient couplings with triethylgermane (Et₃Ge-H) at room temperature, which was enabled by the air- and moisture-stable Pd(I) dimer, [Pd(μ-I)(P^<i>t</i>Bu₃)]₂. The method tolerates numerous functional groups, including valuable (pseudo)halides.