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On Homogeneous Gold/Palladium Catalytic Systems
Author(s) -
Hashmi A. Stephen K.,
Lothschütz Christian,
Döpp René,
Ackermann Martin,
De Buck Becker Janosc,
Rudolph Matthias,
Scholz Christian,
Rominger Frank
Publication year - 2012
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/adsc.201000044
Subject(s) - palladium , chemistry , catalysis , aryl , intramolecular force , allylic rearrangement , organic chemistry , photochemistry , alkyl
Two substrates containing an aryl iodide and an allenoate ester were prepared and the gold‐induced cycloisomerisation to vinylgold(I) species and their proto‐deauration as well as the intramolecular palladium‐catalysed cross‐coupling reactions were investigated. Switching to catalytic amounts of gold and palladium and stoichiometric amounts of silver did indeed furnish the product of a cycloisomerisation/intramolecular cross‐coupling. Control experiments revealed that silver cannot substitute for gold or palladium in these reactions, but a different palladium catalyst in a different oxidation state also afforded the cycloisomerisation/intramolecular cross‐coupling products in only slightly reduced yields. By ICP analysis the palladium was shown to contain gold only at the sub‐ppm level. This shows how carefully results obtained with such systems have to be interpreted. Then a series of allylic and benzylic o ‐alkynylbenzoates were investigated in gold‐ and palladium‐catalysed reactions. For esters of benzyl alcohol and cinnamyl alcohol no palladium co‐catalyst was needed for the conversion. All reagents were thoroughly checked for palladium traces by ICP analysis in order to thoroughly exclude a gold/palladium co‐catalysis. Optimisation of the gold complex, counter ion and solvent showed that gold(I) isonitrile pre‐catalysts and silver triflate as activator in dioxane are suitable to convert a number of substrates with aryl, alkyl and even cyclopropyl substituents. Crossover experiments proved an intermolecular allyl transfer.