Results from a mechanistic study on the Ni(COD)2-bipy-catalyzed alkylation of anhydrides are consistent with turnover-limiting reductive elimination at high Et2Zn concentrations. While the presence of styrene does not affect the initial rate of alkylation, it appears to inhibit catalyst decomposition and provides higher product yield at long reaction times. In contrast, Ni(COD)2-iPrPHOX-catalyzed anhydride alkylation proceeds through two competing catalytic cycles differentiated by the presence of styrene. The presence of styrene in this system appears to accelerate rate-limiting oxidative addition and promotes the cycle which proceeds 4 times more rapidly and with much higher enantioselectivity than its styrene-lacking counterpart.

Treatment of cyclic anhydrides with stoichiometric amounts of nickel-neocuproine complex generates alkylcarboxylato-nickelalactones upon extrusion of CO. These metalacycles undergo cross-coupling with arylzinc reagents. The generated CO is sequestered in situ by a nickel-dppb complex. The overall sequence effects a secondary sp3(electrophile)-sp2(nucleophile) cross-coupling and allows for control of stereochemistry during the bond-forming event.

A general Rh(III)-catalyzed synthesis of naphthyridinone derivatives is described. It relies on a double-activation and directing approach leveraging nicotinamide N-oxides as substrates. In general, high yields and selectivities can be achieved using low catalyst loadings and mild conditions (room temperature) in the couplings with alkynes, while alkenes require slightly more elevated temperatures.

A nickel-catalyzed alkylation of succinic and glutaric anhydrides with alkyl- and arylzinc reagents has been developed. A dramatic olefin effect has been investigated resulting in the identification of several styrene-based promoters which show pronounced enhancements in reaction rate. The substrate scope with respect to electrophilic and nucleophilic coupling partners has been examined and found to be remarkably broad, allowing for rapid introduction of molecular complexity through the use of functionalized coupling partners. Regioselective alkylation of an unsymmetrical succinic anhydride and a profound effect of pendent coordinating olefins on reaction rate suggest a mechanism involving discrete oxidative addition of the nickel complex into the cyclic anhydride followed by a transmetalation event.