Reactions of enols of amides with diazomethane

The reaction of 10 carboxamides activated by two beta-electron-withdrawing groups, which mostly exist completely or partially in their enol forms, with diazomethane was investigated. The main outcome is the diversity of reactions observed. With the most acidic enols 3-7, activated by at least one trifluoroethoxycarbonyl group or a cyano group, O-methylation or O,N-dimethylation takes place. With beta-dimethoxycarbonyl-activated systems 5 and 8, the C-methylation product of the amide form was one of the products. With a Meldrum's acid anilide enol 2, a cleavage took place leading to the C-alkylated imine having a CH(CO(2)Me)(2) group. Exchange of one 2,2,2-trifluoroethoxycarbonyl by a methoxycarbonyl in the C,N-dimethylation product of Me(2)CHNHC(OH)[double bond]C(CO(2)CH(2)CF(3))(2) 4 took place. The 2-anilido-1,3-cyclopentanedione 10 was methylated on a ring carbonyl while the enol of the 1,3-indanedione analogue 11 reacted with three diazomethane molecules and underwent a ring expansion and O-methylation to the 3-anilido-1,4-dimethoxynaphthalene. It is suggested that the reaction initiates by protonation of the diazomethane by the enol and an approximate qualitative relationship exists between the acidity of the enol and K(enol) and the regioselectivity of the reaction.