Di‐ <i>tert</i> ‐Butyl‐Peroxide–CuI Promoted Radical Hydrogermylation of Alkenes

A new protocol for alkene hydrogermylation with hydrogermanes involving a radical chain‐transfer mechanism initiated by di‐ tert ‐butyl peroxide (DTBP) and CuI in methyl tert ‐butyl ether (MTBE) is disclosed. The method has good generality regarding both appropriate alkene substrate‐types and hydrogermanes, and compares well to other existing protocols, sometimes improving them, while being easy‐to‐implement. The developed system is particularly well‐suited for indenes and allows for the preparation of original 2‐germylated indanes through a previously unexplored approach.