Diastereoselectivity in the Carroll rearrangement of β-keto esters of tertiary allylic alcohols

Abstract

Carroll rearrangement of β-keto esters derived from tertiary allylic alcohols, for example, 7, under basic conditions followed by decarboxylation of the resulting β-keto acids yielded the expected γ, δ-unsaturated methyl ketones 8 with a range of olefin geometries from 100:0 to 1:1.8 E/Z, depending on the relative steric requirements of the two groups at the allylic center. © 2003 Elsevier Ltd. All rights reserved.