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Updated: Jul 6, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Construction of highly functionalized diazoacetoacetates via catalytic Mukaiyama-Michael reactions
1Department of Chemistry and Biochemistry, University of Maryland, College Park, MD 20742, USA.
Abstract:
Functionalized diazo acetoacetates are prepared by an efficient Mukaiyama-Michael reaction between methyl 3-(trialkylsilanoxy)-2-diazo-3-butenoate and alpha,beta-unsaturated enones. Vinyl ether and ketone derivatives are both accessible in good to excellent yield through this methodology. The mild Lewis acid zinc(II) triflate is the optimal catalyst, and its loading can be as low as 0.1 mol %. In addition, zinc triflate was also found to be a superior catalyst for the related Mukaiyama-aldol reaction.
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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.
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