15972-89-1Relevant academic research and scientific papers
Cationic η3-allyl complexes. 21. Telomerization of buta-1,3-diene with Z-H compounds mediated by group 10 complexes
Bouachir, Faouzi,Grenouillet, Pierre,Neibecker, Denis,Poirier, Jacques,Tkatchenko, Igor
, p. 203 - 215 (1998)
Cationic (η3-allyl) complexes of general formula [(η3-allyl)M(ligand)2]+Y-, where Y- is a non-coordinating anion (BF4-, ClO4-, BF4-) have been examined in telomerization reactions of buta-1,3-diene with representative nucleophiles. No reaction are observed for nickel complexes, due to their high reactivity versus nucleophiles. With palladium complexes, the reaction only occurs with alcohols and provides an increased selectivity for telomers with more than two diene units, leading to C16, C24 and even higher ethers. Although much less reactive, platinum complexes can also produce higher telomers when hydrogenosilanes are used. It is proposed, at least in the case of palladium, that the formation of C16 and C24 ethers arises from the coupling of C8 units within dimeric palladium intermediates with the telogen acting as a bridging ligand.
Carbonylation of allylic ethers to esters
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, (2008/06/13)
A method is disclosed for the production of esters by reaction of an allylic ether with carbon monoxide in the presence of a catalytically effective amount of a Group VIII noble metal catalyst and halide compound to obtain esters. The halide compound is present in an amount sufficient to prevent the catalyst from being converted into a Group VIII metal during the reaction. When the reaction is conducted in the presence of a quaternary ammonium salt the ester may be extracted by solvent extraction to minimize catalyst decomposition caused when extractive distillation is used to separate the ester.
PREPARATION OF FIVE- AND SIX- MEMBERED CYCLIC KETONES BY THE PALLADIUM-CATALYZED CYCLIZATION REACTION. APPLICATION TO METHYL DIHYDROJASMONATE SYNTHESIS
Tsuji, Jiro,Kobayashi, Yuichi,Kataoka, Hideaki,Takahashi, Takashi
, p. 1475 - 1478 (2007/10/02)
Methyl 3-oxo-8-phenoxy-6-octenoate (1) was cyclized using Pd(OAc)2-PPh3 as a catalyst to give 2-carbomethoxy-3-vinylcyclopentanone (2) and 2-carbomethoxy-4-cycloheptenone (3).The former was the main product in acetonitrile. 2-Alkylated 3-oxo-8-phenoxy-6-octenoates were converted mainly to the five-membered ketones.Based on this cyclization method, methyl dihydrojasmonate (8) was prepared from methyl 2-pentyl-3-oxo-8-phenoxy-6-octenoate (5).Methyl 3-oxo-9-phenoxy-7-nonenoate (10) was subjected to the palladium-catalysed cyclization to afford 2-carbomethoxy-3-vinylcyclohexanone (11) selectively without forming the eight membered ketone (12).
