The Heck reaction of neutral or electron-rich aryl bromides with the 1,1-disubstituted olefins butyl methacrylate and R-methylstyrene catalyzed by Pd nanoparticles in tetrabutylammonium bromide as solvent and tetrabutylammonium acetate as base leads to a prevalent formation of the terminal olefin. In contrast, reaction of p-bromoacetophenone leads to the internal olefin. Whereas the solvent stabilizes the metal nanoclusters, the base is responsible for a fast neutralization of the PdH impeding the hydride readdition to reaction products and avoiding the olefin interconversion. The terminal olefins are efficiently converted into the more stable internal E isomers by using tetrabutylammonium pivalate as catalyst.

Pd Nanoparticle Catalyzed Heck Arylation of 1,1-Disubstituted Alkenes in Ionic Liquids. Study on Factors Affecting the Regioselectivity of the Coupling Process

NACCI, Angelo;MONOPOLI A;
2003-01-01

Abstract

The Heck reaction of neutral or electron-rich aryl bromides with the 1,1-disubstituted olefins butyl methacrylate and R-methylstyrene catalyzed by Pd nanoparticles in tetrabutylammonium bromide as solvent and tetrabutylammonium acetate as base leads to a prevalent formation of the terminal olefin. In contrast, reaction of p-bromoacetophenone leads to the internal olefin. Whereas the solvent stabilizes the metal nanoclusters, the base is responsible for a fast neutralization of the PdH impeding the hydride readdition to reaction products and avoiding the olefin interconversion. The terminal olefins are efficiently converted into the more stable internal E isomers by using tetrabutylammonium pivalate as catalyst.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11586/41141
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