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Methoxycarbonylation versus Hydroacylation of Ethene; Dramatic Influence of the Ligand in Cationic Palladium Catalysis

✍ Scribed by Robert I. Pugh; Eite Drent

Publisher: John Wiley and Sons
Year: 2002
Tongue: English
Weight: 66 KB
Volume: 344
Category: Article
ISSN: 1615-4150
DOI: 10.1002/1615-4169(200209)344:8<837::aid-adsc837>3.0.co;2-1

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✦ Synopsis

The palladium-catalysed carbonylation of ethene in methanol shows acute sensitivity towards the diphosphine ligand used. Systems based on 1,3bis(di-t-butylphosphino)propane afford catalysts for fast, selective methoxycarbonylation to methyl propionate; the corresponding catalyst based on 1,2-bis(di-t-butylphosphino)ethane hydroacylates ethene to diethyl ketone at high rates. The use of less sterically demanding ligands, hydrogen and auxiliary acid are explored and mechanistic implications discussed.