REGIOSELECTIVE PREPARATION OF KINETIC TRIMETHYLSILYL ENOL ETHERS FROM β-KETO SILANES

Asymmetric hetero-ene reactions of trimethylsilyl enol ethers catalyzed by tridentate Schiff base chromium(III) complexes.

Chemo-, regio- and stereoselective preparation of silyl enol ethers from thiol esters and bis(iodozincio)alkane.

Treatment of thiol ester with bis(iodozincio)alkane in the presence of palladium catalyst followed by silylation affords Z-silyl enol ether chemo-, regio- and stereoselectively.

Iridium-catalyzed enantioselective allylation of silyl enol ethers derived from ketones and α,β-unsaturated ketones.

The unified Ir-catalyzed enantioselective allylic substitution reactions of silyl enol ethers derived from ketones and α,β-unsaturated ketones with branched, racemic allylic alcohols are described. This transformation is catalyzed by the Carreira system and proceeds without fluoride, and with high ee and b : l ratio. The synthetic utility of this method was illustrated by the concise enantiosel...

Spiroketals via oxidative rearrangement of enol ethers.

Oxidative rearrangement of cyclic enol ethers leads to alpha-alkoxyesters. In the presence of a neighboring spiroether, this approach provides a stereoselective access to spiroketals. A modified proposal for the biosynthesis of acutumine is presented.

Probing keto-enol tautomerism using photoelectron spectroscopy.

We theoretically investigate the mechanism of tautomerism in the gas-phase acetylacetone molecule. The minimum energy path between the enolone and diketo forms has been computed using the Nudged-Elastic Band (NEB) method within the density-functional theory (DFT) using the projector augmented-wave method and generalized gradient approximation in Perdew-Wang (PW91) parametrization. The lowest tr...