Nickel-Catalyzed Cross-Coupling Reactions of Unreactive Phenolic Electrophiles via C-O Bond Activation

Nickel-catalyzed cross-coupling reactions of aryl esters, carbamates, carbonates, ethers and arenols are reviewed. Carbon-oxygen bonds in these phenol derivatives cannot be activated by palladium, a typical cross-coupling catalyst, but a low valent nickel species in conjunction with a strong sigma-donor ligand is uniquely effective for achieving this. The review is organized primarily by substrate class and secondarily by coupling partners, encompassing organometallics, heteroatom nucleophiles, C-H bonds and many others. Although the reactions in this category are covered thoroughly, each reaction is described only briefly, so that it is possible to quickly overview the spectrum of nickel-catalyzed cross-coupling reactions of inert phenol derivatives. The robustness of inert phenol derivatives under typically used catalytic conditions as well as their utility as a directing group allow unique synthetic applications of these new C-O cross-coupling reactions, which is also included in cases where appropriate. Mechanistic aspects of C-O bond activation by nickel are also summarized, highlighting their diversity compared with the C-X bond activation involved in conventional cross-coupling processes.