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For details, see Electronic Supplementary Information
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Presumably, the H originates either from the PhMe solvent or pcymeneor adventitious water. Similar results were observed when PhMe was substituted with PhH. When substrate 3a was subjected to stoichiometric amounts of [Ru(p-cymene)Cl2]2 and PPh3, product 4a was formed with complete conversion. No Ru-hydrides could beobserved by 1H NMR spectroscopy. Instead, Ru(3a) and Ru(4a) complexes were detected, suggesting that these species are catalyst resting states. For details, see Electronic Supplementary Information.
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84
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70350639427
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J. Choi, Y. Choliy, X. Zhang, T. J. Emge, K. Krogh-Jespersen andA. S. Goldman, J. Am. Chem. Soc., 2009, 131, 15627-15629.
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(2009)
J. Am. Chem. Soc
, vol.131
, pp. 15627-15629
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Choi, J.1
Choliy, Y.2
Zhang, X.3
Emge, T.J.4
Krogh-Jespersen, K.5
Goldman, A.S.6
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86
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79955586723
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Note
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A Fries-type rearrangement involving formation of distinct Ruimidate and benzyltriphenylphosphonium cations via dealkylation is an alternative mechanism. Alkylation of the N atom ofalkoxypyridines is known using activated methylating agents.
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89
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79955611561
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Note
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Based on our crossover studies (Fig. 2), we favor themechanisms highlighted in Fig. 4.
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