Tiffeneau–Demjanov Rearrangement by Using alpha-Chloro-diazo-acetate: A Direct Access to alpha-Chlorinated Medium-Size-Ring Ketones via Ring Enlargement

Maxime Dousset (1) , Karel Le Jeune (1) , Sylvana Cohen (1) , Jean-Luc Parrain (1) , Gaëlle Chouraqui (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

alpha-Chloro(diazo)acetate can be readily used in an intermolecular ring expansion catalyzed by a boron Lewis acid to construct alpha-chlorinated medium-size cyclic ketones. This intermolecular Tiffeneau–Demjanov reaction proceeds in good yield from easily prepared or commercially available starting materials and allows the concomitant formation of a tetrasubstituted stereocenter.

Mots clés: alpha-halogenation; ring expansion; chloro(diazo)acetate; cyclic ketones; tetrasubstituted stereocenter

Domaines: Chimie organique

Maxime Dousset, Karel Le Jeune, Sylvana Cohen, Jean-Luc Parrain, Gaëlle Chouraqui. Tiffeneau–Demjanov Rearrangement by Using alpha-Chloro-diazo-acetate: A Direct Access to alpha-Chlorinated Medium-Size-Ring Ketones via Ring Enlargement. Synthesis: Journal of Synthetic Organic Chemistry, 2016, 48, pp.2396-2401. ⟨10.1055/s-0035-1561413⟩. ⟨hal-01414922⟩