TBAF-Triggered Aldol-Type Addition of alpha-Triethylsilyl-alpha-diazoacetone

Imen Abid (1, 2) , Pascal Gosselin (1) , Monique Mathé-Allainmat (3) , Souhir Abid (4) , Gilles Dujardin (1) , Catherine Gaulon-Nourry (1)

1 IMMM - Institut des Molécules et Matériaux du Mans
2 Université de Sfax - University of Sfax
3 CEISAM - Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation
4 FSS - Faculté des Sciences de Sfax

Aldol-type addition of alpha-triethylsilyl-alpha-diazoacetone was achieved under nucleophilic activation by tetrabutylammonium fluoride (TBAF). The use of a semi-stoichiometric amount of TBAF (protocol P1) provided the corresponding beta-hydroxy-alpha-diazoacetone as the sole product. Alternatively, the use of a catalytic amount of TBAF led to a mixture of beta-hydroxy- and beta-silyloxy-alpha-diazoacetone products, which was cleanly desilylated with Et3N center dot 3HF (protocol P2). The weakly basic conditions employed tolerate a wide range of substrates and constitute a high-yielding, convenient complementary procedure to the low-temperature LDA-promoted aldol-type addition of diazoacetone.

Mots clés: Aldehydes; Aldol reactions; Anions; Degradation; Mixtures

Domaines: Chimie

Imen Abid, Pascal Gosselin, Monique Mathé-Allainmat, Souhir Abid, Gilles Dujardin, et al.. TBAF-Triggered Aldol-Type Addition of alpha-Triethylsilyl-alpha-diazoacetone. Journal of Organic Chemistry, 2015, 80 (20), pp.9980-9988. ⟨10.1021/acs.joc.5b01554⟩. ⟨hal-02141604⟩