Oxymetallation. Part II. The t-butyl peroxymercuration and methoxymercuration of αβ-unsaturated ketones and esters

Abstract

The products of both t-butyl peroxymercuration and methoxymercuration of six αβ-unsaturated ketones and seven αβ-unsaturated esters have been characterised. The structures of the oxymercurials are deduced from their ¹H n.m.r. spectra on the basis of chemical shifts and ¹⁹⁹Hg coupling constants. Where the ketones and esters are alkylated solely at the carbon α to the carbonyl group, the mercury becomes attached to the carbon β to the carbonyl group (β-mercuration); for all other compounds, α-mercuration is obtained. The reactions are compared with other electrophilic additions to αβ-unsaturated carbonyl compounds.