The Claisen condensation reaction is a classical method used for the formation of C−C bonds. Homo‐ and cross‐Claisen condensation reactions are usually carried out using a Ti(IV)‐based reagent at ultra‐low‐temperatures. In this report, intermediate β‐keto acyl imidazoles were synthesised using a sodium imidazolide‐catalysed homo‐ and cross‐condensation reaction of N‐acyl imidazoles performed under mild conditions and subsequently used to prepare a range of β‐keto esters and ketones via alcoholysis or hydrolysis. This method is particularly suitable for the synthesis of isotopically‐labelled acetylacetic ester compounds. N‐acyl imidazole compounds are useful reactants for the Claisen condensation reaction.

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