Palladium-Catalysed Desulfitative Heck Reaction Tolerant to Aryl Carbon-Halogen Bonds for Access to (Poly)halo-Substituted Stilbene or Cinnamate Derivatives

Aymen Skhiri (1, 2) , Ridha Ben Salem (2) , Jean-François Soulé (1) , Henri Doucet (1)

1 ISCR - Institut des Sciences Chimiques de Rennes
2 Université de Sfax - University of Sfax

The palladium-catalysed desulfitative Heck type reaction of (poly)halo-substituted benzenesulfonyl chlorides with alkenes was investigated. Styrene or acrylates in the presence of bromo- or iodobenzenesulfonyl chlorides and a phosphine-free palladium catalyst were found to afford the expected β-arylated Heck type products with complete regio- and stereoselectivities. The reaction tolerates a variety of substituents on the halobenzenesulfonyl chloride. Moreover, no cleavage of the C-Br and C-I bonds was observed in the course of these reactions, allowing further transformations. Using 4-bromobenzenesulfonyl chloride as the central unit, consecutive desulfitative Heck type reaction followed by palladium-catalysed direct arylation allowed to prepare heteroarylated stilbene derivatives in only two steps.

Keywords: Palladium catalyst; halobenzenesulfonyl chlorides; Halogen bonds; Heck reactions; Aromatic compounds; Carbon; Catalysts; Chemical reactions; Chlorine compounds; Hydrocarbons; Olefins; Palladium; Phosphorus compounds; Styrene; Arylations; Central units; Cinnamates; Phosphine-free; Catalysis

Domains: Chemical Sciences; Organic chemistry

Aymen Skhiri, Ridha Ben Salem, Jean-François Soulé, Henri Doucet. Palladium-Catalysed Desulfitative Heck Reaction Tolerant to Aryl Carbon-Halogen Bonds for Access to (Poly)halo-Substituted Stilbene or Cinnamate Derivatives. Synthesis: Journal of Synthetic Organic Chemistry, 2016, 48 (18), pp.3097-3106. ⟨10.1055/s-0035-1560449⟩. ⟨hal-01367223⟩