- 2-pyrimidylphosphines: A new class of ligands for transition metal catalysis
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The synthesis of 2-pyrimidyldiphenylphosphine (2), bis-2- pyrimidylphenyl-phosphine (3) and tris-2-pyrimidylphosphine (4) is described. Ligand 2 forms cationic complexes with palladium(II) in which four-membered P/N-chelates are involved, leading to a ver
- Reetz, Manfred T.,Demuth, Ralf,Goddard, Richard
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- The intriguing methoxycarbonylation of trimethylsilylacetylene in the presence of Drent's catalytic system
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The alkoxycarbonylation of trimethylsilylacetylene has been studied in order to develop an atom economic sustainable synthesis of 2-(trimethylsilyl)acrylates, a family of valuable intermediates. Pd(OAc)2 in combination with CH3SO3H and diphenyl-(pyridin-2-yl)phosphine or diphenyl-(6-methyl-pyridin-2-yl)phosphine is an active catalyst for the reaction affording mixtures of the sought 2-(trimethylsilyl)acrylate and the isomeric 3-(trimethylsilyl)acrylate. The phosphine ligand has a dramatic effect on the reaction. When employing diphenyl-(pyridin-2-yl)phosphine, it is necessary to carry out the reaction at 80°C in order to observe a modest catalytic activity, and the product is an almost equimolecular mixture of the two isomeric esters. On the contrary, when employing diphenyl-(6-methyl-pyridin-2-yl)phosphine, the reaction proceeds under much milder conditions affording with high rate (turnover frequency [TOF] up to 1200 h?1) and selectivity (>95%) of the sought 2-(trimethylsilyl)acrylate. The reaction conditions have been optimized, and the effects of phosphine/palladium, acid/palladium, reaction time, temperature, and CO pressure have been investigated.
- Sole, Roberto,Scrivanti, Alberto,Alam, Md. Mahbubul,Beghetto, Valentina
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- 1,3-DIPOLAR CYCLOADDITION OF BENZONITRILE OXIDE WITH VINYLSILANES
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The reaction of benzonitrile oxide with several vinylsilanes has been found to afford silylated isoxazoles.Relative rates for the cycloaddition reaction were determined.
- Padwa, Albert,MacDonald, J. Gavin
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p. 3219 - 3222
(2007/10/02)
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