Conversion of Primary Alcohols and Butadiene to Branched Ketones via Merged Transfer Hydrogenative Carbonyl Addition–Redox Isomerization Catalyzed by Rhodium
Brian J. Spinello, Jessica Wu, Yoon Cho, Michael J. Krische
Abstract
The first examples of rhodium-catalyzed carbonyl addition via hydrogen autotransfer are described, as illustrated in tandem butadiene-mediated carbonyl addition-redox isomerizations that directly convert primary alcohols to isobutyl ketones. Related reductive coupling-redox isomerizations of aldehyde reactants mediated by sodium formate also are reported. A double-labeling crossover experiment reveals that the rhodium alkoxide obtained upon carbonyl addition enacts redox isomerization without dissociation of rhodium at any intervening stage.
Topics & Concepts
ChemistryRhodiumIsomerizationAldehydePhotochemistryRedoxCatalysisDissociation (chemistry)Alcohol oxidationSodium formateKetoneOrganic chemistryAsymmetric Hydrogenation and CatalysisCarbon dioxide utilization in catalysisCatalytic C–H Functionalization Methods