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18744372130
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For other recent examples of the metal-catalyzed oxidative functionalization of C-H bonds, see: (a) Chen, M. S.; Prabagaran, N.; Labenz, N. A.; White, M. C. J. Am. Chem. Soc. 2005, 127, 6970.
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For representative studies of regioselectivity in stoichiometric cyclopalladation, see: (a) Teijido, B.; Fernandez, A.; Lopez-Torres, M.; Castro-Juiz, S.; Suarez, A.; Ortigueira, J. M.; Vila, J. M.; Fernandez, J. J. J. Organomet. Chem. 2000, 598, 71.
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3042704672
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2O (1:5.5)]. This preference for A (in comparison to the analogous C-H activation/olefin additions) may be due to the high CO pressures (5-20 atm) used in these experiments, which are expected to limit the open sites at Ru for weak secondary coordination interactions. (a) Asaumi, T.; Matsuo, T.; Fukuyama, T.; Ie, Y.; Kakiuchi, F.; Chatani, N. J. Org. Chem. 2004, 69, 4433.
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Rh-catalyzed C-H activation/alkylation of aldimines proceeds to afford A as the major regioisomer with good selectivity except when X = F (A:B = 1:3). Lim, Y.-G.; Han, J.-S.; Koo, B. T.; Kang, J.-B. J. Mol. Catal. A 2004, 209, 41.
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For Ru-catalyzed pyridine-directed C-H activation/arylation, see: Oi, S.; Fukita, S.; Hirata, N.; Watanuki, N.; Miyano, S.; Inoue, Y. Org. Lett. 2001, 3, 2579.
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note
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1H NMR spectroscopy). See Supporting Information for full details.
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35
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0033997284
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II, see: (a) Fox, J. M.; Huang, X.; Chieffi, A.; Buchwald, S. L. J. Am. Chem. Soc. 2000, 122, 1360.
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Canty, A. J.; Minchin, N. J.; Skelton, B. W.; White, A. H. J. Chem. Soc., Dalton Trans. 1987, 1477.
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25444462452
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see refs 8 and 9
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0-catalyzed reactions and similar arguments have been invoked in these systems (see refs 8 and 9).
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39
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25444500125
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note
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2 to form the diacetoxylated product at similar rates. Therefore, the observed selectivity appears to be inherent to the C-H activation reaction of 18 (rather than resulting from selective consumption of one of the regioisomers after it is formed).
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40
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25444491437
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see ref 5d,g and refs 8-10
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The regioselectivity of transition metal-mediated C-H activation reactions is frequently dominated by steric effects. For example, see ref 5d,g and refs 8-10.
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