TIPS-Diazoacetone Aldol Addition: Mechanistic Aspects and Contribution to the Synthesis

• DOI: 10.1021/acs.joc.0c02725
• Publication Date: 2021-03-17T13:24:15Z
• Authors: Sigrid Gavelle; Imen Abid; Bohdan Biletskyi; Sylvain Henrion; Annie Hémon-Ribaud; Jérôme Lhoste; Arnaud Martel; Gilles Dujardin; Catherine Gaulon-...
• Keywords: 01 natural sciences; 0104 chemical sciences

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.