Exploiting Ancillary Ligation To Enable Nickel-Catalyzed C–O Cross-Couplings of Aryl Electrophiles with Aliphatic Alcohols

Abstract

The use of (L)Ni(o-tolyl)Cl precatalysts (L = PAd-DalPhos or CyPAd-DalPhos) enables the C(sp²)–O cross-coupling of primary, secondary, or tertiary aliphatic alcohols with (hetero)aryl electrophiles, including unprecedented examples of such nickel-catalyzed transformations employing (hetero)aryl chlorides, sulfonates, and pivalates. In addition to offering a competitive alternative to palladium catalysis, this work establishes the feasibility of utilizing ancillary ligation as a complementary means of promoting challenging nickel-catalyzed C(sp²)–O cross-couplings, without recourse to precious-metal photoredox catalytic methods.