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Ligand-Dependent Catalytic Cycle and Role of Styrene in Nickel-Catalyzed Anhydride Cross-Coupling: Evidence for Turnover-Limiting Reductive Elimination
journal contribution
posted on 2007-03-07, 00:00 authored by Jeffrey B. Johnson, Eric A. Bercot, John M. Rowley, Geoffrey W. Coates, Tomislav RovisResults 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.