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Updated: Nov 12, 2025

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
TIPS-Diazoacetone Aldol Addition: Mechanistic Aspects and Contribution to the Synthesis
Sigrid Gavelle1, Imen Abid1, Bohdan Biletskyi1
1Institut des Molécules et Matériaux du Mans, IMMM UMR 6283 CNRS - Le Mans Université, Avenue Olivier Messiaen, 72085 CEDEX 9 Le Mans, France.
Abstract:
Aldol addition of α-triisopropylsilyl-α-diazoacetone (TIPS-diazoacetone), promoted by excess lithium diisopropylamide (LDA), was developed and applied to the synthesis of original C-TIPS diazoaldols, C-TIPS diazoketols, and a related Mannich-type product. An unprecedented mechanistic pathway has been proposed, involving a lithiated triazene intermediate resulting from the nucleophilic addition of LDA on the diazo moiety, supported by experimental results and DFT calculations.
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