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Beletskaya has recently shown that a wide variety of five-and six-membered palladacycles including CN and CO types, can serve as catalysts precursors in the arylation of olefins by iodo-and bromoarenes: I. P. Beletskaya, A. N. Kashin, N. B. Karlstedt, A. V. Mitin, A. V. Cheprakov, G. M. Kazankov, J. Organomet. Chem. 2001, 622, 89-96.
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0348205425
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note
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Phenyl triflate gave very poor yields (25% conversion with methyl acrylate and 0.25 mol % of 16d). Diazonium salts like 4-bromobenzenediazonium tetrafluoroborate afforded higher conversions but together with high yields of phenyl bromide under similar conditions.
-
-
-
-
54
-
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0346944817
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-
note
-
Commercially available solvents were used without further purification and no change in efficiencies or yields were detected when the reaction was carried out under nitrogen atmosphere.
-
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55
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0034595666
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Similar catalytic activities have been recently obtained for hydroarylation reactions: J. M. Brunel, A. Heumann, G. Buono, Angew. Chem. Int. Ed. 2000, 39, 1946-1949.
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0348205423
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note
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3.
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58
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0034619245
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Similar behavior has been previously observed for cyclopalladated imine catalysts: M. Nowotny, U. Hanefeld, H. van Koningsveld, T. Maschmeyer, Chem. Commun. 2000, 1877-1878.
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0346944818
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-
note
-
One of the referees kindly suggested that the fact that the TOF becomes higher at lower catalyst loadings strongly suggests an equilibrium between monomeric Pd, which is the actual catalyst, with the palladium nanoparticles. At lower initial Pd concentrations this equilibrium will be shifted to the monomeric form, increasing the TOF.
-
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-
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60
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0035959456
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For very recent review about Heck chemistry of aryl bromides and chlorides, see: N. J. Whitcombe, K. K. M. Hii, S. E. Gibson, Tetrahedron 2001, 57, 7449-7476.
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0346944816
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note
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-1) and with a very low 22% yield. Better yield (69%) is obtained with higher catalyst loadings (TON = 690).
-
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73
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33744870975
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For a review about annulation reactions, see: R. C. Larock, J. Organomet. Chem. 1999, 576, 111-124.
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Larock, R.C.1
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0348205421
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-
note
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[6c].
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-
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