C- and O-alkylation with alpha-haloketones of the adamantane series

Reactions of 1-adamantyl bromomethyl ketone and 1-(1-adamantyl)-3-bromo-2-p ropanone with acetylacetone and ethyl acetoacetate in a mixture of dry diet hyl ether with anhydrous methanol in the presence of sodium methoxide affor ded 3-(1-adamantylcarbonylmethyl)-2,4-pentanedione, ethyl 2-(1-adamantylcar bonylmethyl)-3-oxobutanoate, 4-acetyl-1-(1-adamantyl)-2,5-hexanedione and e thyl 2-acetyl-5-(1-adamantyl)-4-oxopentanoate. The Knoevenagel-Cope reactio ns of 1-adamantyl bromomethyl ketone and 1-(1-adamantyl)-3-bromo-2-propanon e with diethyl malonate yielded, respectively, diethyl 1-(1-adamantyl)-2-br omoethylidenemalonate and diethyl 1-(1-adamantylmethyl)-2-bromoethylidenem O-Alkylation of ethyl acetoacetate with 1-adamantyl bromomethyl ketone gave ethyl 3-(1-adamantylcarbonylmethoxy)-2-butenoate. Carboxylic acids reacted with 1-adamantyl bromomethyl ketone to form the corresponding 2-(1-adamant yl)-2-oxoethyl carboxylates.