Indium-Mediated 2-Oxonia Cope Rearrangement of 1,4-Dienols to 1,3-Dienols

Abstract

An indium-mediated isomerization of 1,4-dienols to 1,3-dienols is described. This procedure consists of the addition of pentadienylindium, in a protic solvent, to aldehydes giving the kinetic ?-allylation product in high yields. The subsequent conversion of this ?-allylation product to its thermodynamic 1,3-dienol a-isomer can be achieved by its exposure to indium triflate in the presence of a substoichiometric amount of aldehyde at room temperature. This transformation exhibited moderate to good substrate scope and has been shown to proceed by a 2-oxonia Cope rearrangement.

• Acceptance Date: Dec 25, 2018
• Publication Date: Jan 9, 2019
• Journal: ACS Omega
• Publisher: American Chemical Society
• Pages: 785 -792
• DOI: https://doi.org/10.1021/acsomega.8b03118
• Keywords: Addition reaction; Carbonyl compounds (organic); Catalysts; Physical and chemical processes
• Publisher URL: https://doi.org/10.1021/acsomega.8b03118