Abstract

AbstractAcyclic and cyclic unsymmetrical ketones 1 are regioselectively acylated via their corresponding metalated dimethyl‐hydrazones 3 by using acid chlorides or anhydrides, arylnitriles, ethyl formate, carbon disulfide/methyl iodide, alkyl chloroformates, dialkyl carbonates, phenyl isocyanate, or phenyl isothiocyanate as acylating agents. Subsequent acidic hydrolysis leads to the 1,3‐diketones 6 in acceptable to excellent overall yields. The tautomeric structure of the product hydrazones 4, 5, 7, and 8 is determined. Cyanation of 3 with cyanogen bromide affords the α‐cyano dimethylhydrazones 9.

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