Palladium-catalyzed alkylation of allylic nitrates derived from ceric ammonium nitrate promoted oxidative addition of trimethylsilyloxy-cyclopropanes to 1,3-butadiene

Article abstract of DOI:10.1016/S0040-4039(00)73745-2

Silyloxycyclopropanes are easily oxidized by eerie ammonium nitrate to generate β-carbonylalkyl radicals which are able to add to 1,3-butadiene to give a mixture of 4-(γ-carbonylalkyl)-substituted 3-nitroxy-1-butenes and 4-(γ-carbonylalkyl) substituted (E)-1-nitroxy-2-butenes (1,2- and 1,4-adducts) in ca. 1:1 molar ratio. The crude mixture, subjected to palladium-catalyzed alkylation by a variety of carbon nucleophiles, affords mainly δ,g3-unsaturated carbonyl compounds with high regio- and stereoselectivity and in satisfactory overall yield.