Mechanism of the oxidative carbonylation of terminal alkynes at the ≡C-H bond in solutions of palladium complexes
摘要：
The formation mechanism of the active catalyst in the oxidative carbonylation of terminal alkynes at the ≡C-H bond has been investigated for the catalytic system Pd(OAc) 2 -PPh 3 - p -benzoquinone (Q)-MeOH. It has been demonstrated by NMR spectroscopy, X-ray crystallography, and kinetic measurements that the catalytically active palladium is in the oxidation state 0 and is bound into complexes stabilized by p -benzoquinone (PdL 2 Q, where L = PPh 3 ). A mechanism is suggested for the catalytic process, which includes the formation of the complex PdL 2 Q, the oxidative addition of the alkyne to this complex at the ≡C-H bond, the insertion of CO into the Pd-C bond, and steps in which hydride hydrogen is intramolecularly transferred to the p -quinone.
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关键词：
other bioactive products ring closure reactions diastereoselective syntheses, enantioselective syntheses (incl. cis/trans‐isomerism
DOI：
10.1134/S0023158407020073
被引量：
年份：
2007
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