Efficient macrocyclization using methylene-tethered terminal dienes and bis(manganese(III)-enolate)s

Abstract

Macrocyclic compounds, which have two fused dihydrofuran rings, were synthesized with complete control by the oxidation of α,α,ω,ω-tetraaryl-α,(ω-1)-alkadienes 1 x with manganese(III)-oligomethylenebis(enolate) complexes directly formed by the reaction of the oligomethylene bis(3-oxobutanoate)s 2 y with manganese(III) acetate in situ. The oxamethylene-tethered macrodiolides 5 and 7 were also produced in good to moderate yields by a similar oxidation. The key intermediate, an electron donor–acceptor-like complex, was proposed for the efficient macrocyclization reaction.