Silicon-Controlled Allylation of 1,3-Dioxo Compounds by Use of Allyltrimethylsilane and Ceric Ammonium Nitrate

Article abstract of DOI:10.1021/jo00109a016

A new method was developed for allylation of 1,3-diketones, β-keto esters, and malonates.Treatment of those 1,3-dioxo compounds with allyltrimethylsilane (1.3 equiv) in the presence of ceric ammonium nitrate (2.1 equiv) in methanol at room temperature often gave the mono-C-allylated products in good to excellent yields (74-98percent).These reactions, involving β-carboradical and β-carbocationic intermediates, were controlled by a silyl group.Replacement of ceric ammonium nitrate and methanol with manganese(III) acetate (2.4 equiv) and acetic acid afforded silicon-containing dihydrofurans in high yields at 80 deg C.