C-Acylation of enolates

4 real reactions from the literature, on aryl ketones, six-membered cyclic ketones and methyl ketones. Each scheme shows starting materials, conditions and products, with the yield and reference where the source reports them.

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1. Enolate C-acylation: propionyl chloride (an acid chloride) and cyclohexanone (a six-membered cyclic ketone) with TsOH; EtOH gives 2-propanoylcyclohexan-1-one (the 1,3-diketone). 85% yield.

   Enolate C-acylationChem. Ber. 1957, 90, 2833

2. Enolate C-acylation: phthalimidoacetone (a methyl ketone) with NaOMe gives 3-acetyl-2,3-dihydroisoquinoline-1,4-dione (the 1,3-diketone).

   Enolate C-acylationRealOChem worksheet

3. Enolate C-acylation: an aryl ketone and dimethyl oxalate (an ester) with NaH, DMF, MeOH (same reactants as K) gives the 1,3-dicarbonyl compound. 60% yield.

   Enolate C-acylationJ. Am. Chem. Soc. 1968, 90, 439

4. Enolate C-acylation: an aryl ketone and dimethyl oxalate (an ester) with NaH, DMF, MeOH gives the 1,3-dicarbonyl compound. 45% yield.

   Enolate C-acylationJ. Am. Chem. Soc. 1968, 90, 439