The carbonylation of 2,3-dienylamines proceeds efficiently in the presence of a catalytic system consisting of tris(dibenzylideneacetone)dipalladium(0), 1,3-bis(diphenylphosphino)propane, and p-toluenesulfonic acid, affording α-vinylacrylamides in 59-84% isolated yield. The insertion of carbon monoxide occurs in a regioselective manner at the central sp carbon of the allene unit. The carbonylation reactions of 4-monosubstituted 2,3-dienylamines are stereoselective exclusively affording the α,β-E isomer. This reaction proceeds via π-allylpalladium intermediates, in which the π-allylpalladium unit is directly connected to the double bond. This method is useful for the prepn. of α-vinylacrylamides. In addn., it demonstrates the selective insertion of carbon monoxide into a carbon-nitrogen bond of acyclic amines.
Palladium-Catalyzed RegioselectiveCarbonylation of 2,3-Dienylamines tor-Vinylacrylamides
VASAPOLLO, Giuseppe;
1996-01-01
Abstract
The carbonylation of 2,3-dienylamines proceeds efficiently in the presence of a catalytic system consisting of tris(dibenzylideneacetone)dipalladium(0), 1,3-bis(diphenylphosphino)propane, and p-toluenesulfonic acid, affording α-vinylacrylamides in 59-84% isolated yield. The insertion of carbon monoxide occurs in a regioselective manner at the central sp carbon of the allene unit. The carbonylation reactions of 4-monosubstituted 2,3-dienylamines are stereoselective exclusively affording the α,β-E isomer. This reaction proceeds via π-allylpalladium intermediates, in which the π-allylpalladium unit is directly connected to the double bond. This method is useful for the prepn. of α-vinylacrylamides. In addn., it demonstrates the selective insertion of carbon monoxide into a carbon-nitrogen bond of acyclic amines.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
