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DDC: 540 × Type: Text × Subject: Alkoxycarbonylation ×

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Now showing 1 - 3 of 3
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    Cooperative catalytic methoxycarbonylation of alkenes: Uncovering the role of palladium complexes with hemilabile ligands
    (Cambridge : RSC, 2018) Dong, Kaiwu; Sang, Rui; Wei, Zhihong; Liu, Jie; Dühren, Ricarda; Spannenberg, Anke; Jiao, Haijun; Neumann, Helfried; Jackstell, Ralf; Franke, Robert; Beller, Matthias
    Mechanistic studies of the catalyst [Pd2(dba)3/1,1′-bis(tert-butyl(pyridin-2-yl)phosphanyl)ferrocene, L2] for olefin alkoxycarbonylation reactions are described. X-ray crystallography reveals the coordination of the pyridyl nitrogen atom in L2 to the palladium center of the catalytic intermediates. DFT calculations on the elementary steps of the industrially relevant carbonylation of ethylene (the Lucite α-process) indicate that the protonated pyridyl moiety is formed immediately, which facilitates the formation of the active palladium hydride complex. The insertion of ethylene and CO into this intermediate leads to the corresponding palladium acyl species, which is kinetically reversible. Notably, this key species is stabilized by the hemilabile coordination of the pyridyl nitrogen atom in L2. The rate-determining alcoholysis of the acyl palladium complex is substantially facilitated by metal-ligand cooperation. Specifically, the deprotonation of the alcohol by the built-in base of the ligand allows a facile intramolecular nucleophilic attack on the acyl palladium species concertedly. Kinetic measurements support this mechanistic proposal and show that the rate of the carbonylation step is zero-order dependent on ethylene and CO. Comparing CH3OD and CH3OH as nucleophiles suggests the involvement of (de)protonation in the rate-determining step.
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    Novel ruthenium-catalyst for hydroesterification of olefins with formates
    (London [u.a.] : Royal Society of Chemistry, 2014) Profir, I.; Beller, M.; Fleischer, I.
    An alternative ruthenium-based catalyst for the hydroesterification of olefins with formates is reported. The good activity of our system is ensured by the use of a bidentate P,N-ligand and ruthenium dodecacarbonyl. A range of formates can be used for selective alkoxycarbonylation of aromatic olefins. In addition, the synthesis of selected aliphatic esters is realized. The proposed active ruthenium complex has been isolated and characterized.
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    Promoters for Pd-catalyzed methoxycarbonylation of vinyl acetate
    (Zürich : ARKAT, 2012) Shuklov, I.A.; Dubrovina, N.V.; Schulze, J.; Tietz, W.; Kühlein, K.; Börner, A.
    A study on the influence of acidic and non-acidic promoters for Pd(PPh 3)-catalyzed methoxycarbonylation of vinyl acetate was conducted in order to find an efficient protocol for the synthesis of methyl O-acetyl lactate. Besides known promoters also some new catalytic systems were tested. Aluminium triflate is the most active additive.