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Transition metal–catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp3)–O functionalization step have precluded general methods. Here, we describe computationally guided transition metal–ligand design that positions a hydrogen-bond acceptor anion at the reactive site to promote functionalization. A general cross-coupling of primary, secondary, and tertiary aliphatic alcohols with terminal olefins to furnish >130 ethers is achieved. The mild conditions tolerate functionality that is prone to substitution, elimination, and epimerization and achieve site selectivity in polyol settings. Mechanistic studies support the hypothesis that the ligand’s geometry and electronics direct positioning of the phosphate anion at the π-allyl-palladium terminus, facilitating the phosphate’s hydrogen-bond acceptor role toward the alcohol. Ligand-directed counteranion positioning in cationic transition metal catalysis has the potential to be a general strategy for promoting challenging bimolecular reactivity. [ABSTRACT FROM AUTHOR]