CgPhen-DalPhos Enables the Nickel-Catalyzed O‑Arylation of Tertiary Alcohols with (Hetero)Aryl Electrophiles

While the Ni-catalyzed cross-coupling of primary or secondary aliphatic alcohols and (hetero)­aryl electrophiles is known, related cross-couplings involving tertiary aliphatic alcohols, with a broad scope, are challenging. Herein we disclose that a NiII precatalyst featuring the ligand CgPhen-DalPhos is unusual in its ability to promote the C–O cross-coupling of tertiary aliphatic alcohols with (hetero)­aryl halides (Cl, Br, and I) or phenol derivatives (OMs and OPiv). An exploration of substrate scope and competition experiments help to shed light on the capabilities and reactivity preferences of this catalyst system.