Oxidative methoxycarbonylation of propyne and allene with carbon monoxide and methanol in the presence of copper-palladium catalyst
A direct oxidative methoxycarbonylation of propyne with carbon monoxide in methanol medium in the presence of copper-palladium catalytic system results in methyl 2-butynoate in 18-31% yield. Depending on reaction conditions allene provides either a mixture of methyl 2-(chloromethyl)acrylate and methyl 2-(methoxymethyl)acrylate (~3-4:1) in overall yield 16-23%, or methyl 2-(methoxymethyl)acrylate in 19% yield.
Mal'kina,Kudyakova,Nosyreva,Afonin,Trofimov
p. 1088 - 1092
(2007/10/03)
Elimination of β-palladium hydroxide in the PdII-catalyzed reaction of methyl(α-hydroxymethyl)acrylate with alcohols
Exclusive elimination of β-Pd-OH takes place in the oxypalladation intermediate derived from methyl(α-hydroxymethyl)acrylate and alcohols with PdCl2 catalyst, and no β-Pd-H elimination occurs. Key words: Palladium; Hydroxide; Catalysis; Alkene; Mechanism