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note
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1H NMR were identical to authentic samples.
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33
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A small amount of biphenyl identified in the reaction correlates with the number of surface palladium atoms and suggests that the phenylboronic acid plays a role in reducing the surface palladium. Thus, reactions are performed with a 20% excess of aryl boronic acid.
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(a) 2-Propanol is used as reducing reagent in homo-coupling of aryl halides. See: Hassan, J.; Penalva, V.; Lavenot, L.; Gozzi, C.; Lemaire, M. Tetrahedron 1998, 54, 13793-13804.
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(b) Postreaction NMR of the ethanol solvent revealed a complex mixture including the presence of aldehydic protons (δ 9.74, q, J = 2.5 Hz) indicating oxidation of ethanol.
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0028261953
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This is analogous to the acceleration of oxidative addition of aryl chlorides to Pd(0) via coordination of an electron-withdrawing tricarbonylchromium group to the arene ring. See: Uemura, M.; Nishimura, H.; Kamikawa, K.; Nakayama, K.; Hayashi, Y. Tetrahedron Lett. 1994, 35, 1909-1912.
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For the reaction of p-chloronitrobenzene with phenylboronic acid at 80°C with 5 mol % of Pd/C, after filtration through 0.45 mm filter, we found 1.0 ppm of palladium by atomic absorption spectroscopy. If the reaction were to occur exclusively on palladium that leached into solution, a turnover number (TON) of 16 000 would be required. Catalytic palladium-catalyzed cross-couplings with TON greater than 10000 have only been demonstrated in few cases ((a) Murray, W. V. Chemtracts-Org. Chem. 1993, 6, 263-284.
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