Mechanistic features of isomerizing alkoxycarbonylation of methyl oleate
| Autor: | Luigi Cavallo, Heiko M. Möller, Philipp Roesle, Lucia Caporaso, Christoph J. Dürr, Stefan Mecking |
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| Jazyk: | angličtina |
| Rok vydání: | 2012 |
| Předmět: |
Olefin fiber
Molecular Structure Hydride Esters Oleic Acids Stereoisomerism General Chemistry Biochemistry Medicinal chemistry Catalysis chemistry.chemical_compound Colloid and Surface Chemistry chemistry Propane Pyridine ddc:540 Organic chemistry Quantum Theory Thermodynamics Methanol Trifluoromethanesulfonate Isomerization Stoichiometry |
| Popis: | The weakly coordinated triflate complex [(P^P)Pd(OTf)](+)(OTf)(-) (1) (P^P = 1,3-bis(di-tert-butylphosphino)propane) is a suitable reactive precursor for mechanistic studies of the isomerizing alkoxcarbonylation of methyl oleate. Addition of CH(3)OH or CD(3)OD to 1 forms the hydride species [(P^P)PdH(CH(3)OH)](+)(OTf)(-) (2-CH(3)OH) or the deuteride [(P^P)PdD(CD(3)OD)](+)(OTf)(-) (2(D)-CD(3)OD), respectively. Further reaction with pyridine cleanly affords the stable and isolable hydride [(P^P)PdH(pyridine)](+)(OTf)(-) (2-pyr). This complex yields the hydride fragment free of methanol by abstraction of pyridine with BF(3)·OEt(2), and thus provides an entry to mechanistic observations including intermediates reactive toward methanol. Exposure of methyl oleate (100 equiv) to 2(D)-CD(3)OD resulted in rapid isomerization to the thermodynamic isomer distribution, 94.3% of internal olefins, 5.5% of α,β-unsaturated ester and |
| Databáze: | OpenAIRE |
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