Related Experiment Video
Updated: May 9, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Reactions of enols of amides with diazomethane
1Department of Organic Chemistry, The Hebrew University, Jerusalem 91904, Israel.
Abstract:
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.
Related Concept Videos
Aldehydes and Ketones with Amines: Imine and Enamine Formation Overview
Carboxylic Acids to Methylesters: Alkylation using Diazomethane
Preparation of Amides
The DCC-promoted synthesis of amides begins with the protonation of DCC by carboxylic acid. The protonation makes it a better acceptor. Next, the addition of carboxylate to the protonated carbodiimide gives a reactive acylating agent.
Subsequently, the amine acts as a nucleophile that attacks the acylating agent to form a tetrahedral intermediate. In the...
Reactivity of Enols
1° Amines to Diazonium or Aryldiazonium Salts: Diazotization with NaNO2 Mechanism
Aldehydes and Ketones with Amines: Enamine Formation Mechanism

