A Unified Strategy Toward 5-, 6-, and 7-Membered Nitrogen Heterocycles Through Free Radical then Metal-Mediated Functionalization of Ene-carbamates

Rédouane Beniazza (1) , Clément Poittevin (1) , Jonathan Lusseau (1) , Stéphane Massip (2) , Frédéric Robert (1) , Yannick Landais (1)

1 ISM - Institut des Sciences Moléculaires
2 IECB - Institut Européen de Chimie et Biologie

Free-radical carbo-alkenylation of N-aryl, N-benzyl, and N-phenethyl-ene-carbamates with a disulfone provides vinylsulfones which may then be functionalized and engaged in Heck-type coupling to furnish highly substituted 5-, 6-and 7-membered nitrogen heterocycles. Grignardmediated cyclization starting from the same substrates further allowed a nucleophilic cascade process, affording a straightforward access to hydrocarbazoles, which may be regarded as potent intermediates for the synthesis of alkaloids of the aspidosperma family.

Mots clés: Heterocycle; Heck reaction; Grignard; Vinylsulfones; Cyclization

Domaines: Chimie organique

Rédouane Beniazza, Clément Poittevin, Jonathan Lusseau, Stéphane Massip, Frédéric Robert, et al.. A Unified Strategy Toward 5-, 6-, and 7-Membered Nitrogen Heterocycles Through Free Radical then Metal-Mediated Functionalization of Ene-carbamates. Advanced Synthesis and Catalysis, 2017, 359 (18), pp.3217-3225. ⟨10.1002/adsc.201700485⟩. ⟨hal-03104344⟩