Reactions of fused and unfused α-pyrones with magnesium alkoxide, sodium alkoxide and water as the nucleophile: effects of chelation

Abstract

The reactions between a series of α-pyrones (two mono- and three fused) and the non-chelating base sodium alkoxide, the chelating base magnesium alkoxide and water as the nucleophile, have been studied. Aromatic and other products formed reflect the points of attack on the pyrone systems and when sodium methoxide is used the ensuing cyclisation is preferentially by aldol mechanisms. The employment of excess magnesium methoxide or ethoxide gives magnesium-chelated precursors and the nature of products now depends on these intermediates, and the protection afforded by such magnesium chelation to the reaction products. In the case of structures containing chelated β-keto ester features the chelates are screened from attack as aldol acceptors, but are effective Claisen acceptors. In such chelates an adjacent methylene is activated by further magnesium alkoxide to act as an aldol or Claisen donor. These contrasting aldol/Claisen reactivities, as between a non-chelating and a chelating base, are illustrated in the ensuing chemistry of the pyrones. Treatment with water releases the main carbon chain with decarboxylation, from which new products may form.