Palladium-Catalyzed Addition of 1,3-Diones to Ynamides: An Entry to Alkoxy-Substituted Enamides

Lionel V. Graux (1) , Hervé Clavier (1) , Gérard Buono (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

A new metal-catalyzed addition reaction of 1,3-diketones to ynamides, which provides access to unprecedented alkoxy- substituted enamides, is disclosed herein. A screening of cata- lytic systems showed that both a phosphapalladacycle and a cationic gold complex were capable of promoting this reac- tion rapidly and cleanly. The scope investigation revealed that variously substituted terminal ynamides and cyclic 1,3-diones were well tolerated. The use of internal ynamides led to the formation of both E and Z isomers with low to good selectivi- ties. The proposed mechanism suggests that the phosphapalla- dacycle acts as a p Lewis acid to activate the ynamide.

Domaines: Catalyse; Chimie organique

Lionel V. Graux, Hervé Clavier, Gérard Buono. Palladium-Catalyzed Addition of 1,3-Diones to Ynamides: An Entry to Alkoxy-Substituted Enamides. ChemCatChem, 2014, 6 (9), pp.2544 - 2548. ⟨10.1002/cctc.201402398⟩. ⟨hal-01409701⟩