Nature Communications, Published online: 15 June 2026; doi:10.1038/s41467-026-74317-0 1,n-Difunctionalized alkyl linchpins are valuable synthetic intermediates, but current routes suffer from poor step economy and limited functional group tolerance. Here, the authors report a radical-mediated bidirectional C–C bond cleavage strategy that transforms cyclic ketones into diverse functionalized linchpins via gem-diperoxide intermediates.