C-acylation of tertiary enolates via dithioesters

C-acylation of tertiary enolates via dithioesters Article

Kende, AS, Becker, DA. (1982). C-acylation of tertiary enolates via dithioesters . 12(11), 829-832. 10.1080/00397918208065959

The acylation of unsymmetrical ketones to β-ketoesters at a tertiary enolate center can be selectively achieved by way of the stable β-dithioketoesters (eg, 2). These undergo one-step or sequential conversion to the β-ketoesters using Hg0-BF3. The C-acylation of a ketone by a dialkyl carbonate in the presence of an alkali metal alkoxide is a valuable route to β-ketoesters. This reaction generally fails, however, when the acylation is carried out at a tertiary site, since the driving force of β-ketoester enolate formation is not available in that instance:1. © 1982, Taylor & Francis Group, LLC. All rights reserved.