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

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 bee...

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Bibliographic Details
Published in:Journal of organic chemistry 2021-04, Vol.86 (7), p.4917-4931
Main Authors: Gavelle, Sigrid, Abid, Imen, Biletskyi, Bohdan, Henrion, Sylvain, Hémon-Ribaud, Annie, Lhoste, Jérôme, Martel, Arnaud, Dujardin, Gilles, Gaulon-Nourry, Catherine
Format: Article
Language:English
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Chemical Sciences
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.0c02725