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Catalytic, Nucleophilic Allylation of Aldehydes with 2‑Substituted Allylic Acetates: Carbon–Carbon Bond Formation Driven by the Water–Gas Shift Reaction

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journal contribution
posted on 03.07.2014, 00:00 by Scott E. Denmark, Zachery D. Matesich
The ruthenium-catalyzed allylation of aldehydes with allylic acetates has been expanded to incorporate substituents at the 2-position of the allylic components. Allylic acetates bearing a variety of substituents (CO2-t-Bu, COMe, Ph, CH­(OEt)2, and Me) undergo high-yielding additions with aromatic, α,β-unsaturated, and aliphatic aldehydes. The conditions of the reaction were found to be mild (75 °C, 24–48 h) and only required the use of 2–3 mol % of the triruthenium dodecacarbonyl catalyst under 40–80 psi of CO. The stoichiometries of water and allylic acetate employed were found to be critical to reaction efficiency.