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Methoxycarbonylation versus Hydroacylation of Ethene; Dramatic Influence of the Ligand in Cationic Palladium Catalysis
Author(s) -
Pugh Robert I.,
Drent Eite
Publication year - 2002
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/1615-4169(200209)344:8<837::aid-adsc837>3.0.co;2-1
Subject(s) - chemistry , carbonylation , catalysis , ligand (biochemistry) , palladium , cationic polymerization , medicinal chemistry , steric effects , organic chemistry , propane , hydroacylation , ketone , methanol , carbon monoxide , rhodium , biochemistry , receptor
The palladium‐catalysed carbonylation of ethene in methanol shows acute sensitivity towards the diphosphine ligand used. Systems based on 1,3‐bis(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.