biostudies-literatureSpinello BJWelch FoundationNational Institute of General Medical SciencesNIGMS NIH HHS13507-13512https://www.ebi.ac.uk/biostudies/studies/S-EPMC8739284biostudies-literatureUnknown143(34)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.Journal of the American Chemical SocietyConversion of Primary Alcohols and Butadiene to Branched Ketones via Merged Transfer Hydrogenative Carbonyl Addition-Redox Isomerization Catalyzed by Rhodium.PMC8739284R01 GM069445RO1-GM069445F-0038Wu JCho YSpinello BJKrische MJfalseConversion of Primary Alcohols and Butadiene to Branched Ketones via Merged Transfer Hydrogenative Carbonyl Addition-Redox Isomerization Catalyzed by Rhodium.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.2021-01-01T00:00:00Z2021 Sep2024-11-10T06:25:52.268Z2024-11-10T06:25:52.268ZS-EPMC87392843441515910.1021/jacs.1c07230