Journal of the American Chemical Society · 2008 · 405 citations · 27 references
Chemical EngineeringEngineeringAlkene MetathesisCatalyzed HydrozincationOrganozinc ReagentOrganic ChemistryOrganometallic CatalysisCatalysisMolecular CatalysisChemistryNickel-catalyzed Reductive CarboxylationCatalytic Synthesis
A nickel-catalyzed reductive carboxylation of styrenes using CO2 has been developed. The reaction proceeds under mild conditions using diethylzinc as the reductant. Preliminary data suggests the mechanism involves two discrete nickel-mediated catalytic cycles, the first involving a catalyzed hydrozincation of the alkene followed by a second, slower nickel-catalyzed carboxylation of the in situ formed organozinc reagent. Importantly, the catalyst system is very robust and will fixate CO2 in good yield even if exposed to only an equimolar amount introduced into the headspace above the reaction.
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