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Just before submission of this paper, the same authors have reported the extension of the reaction based on the use of the nitrosoarenes to the synthesis of N-methoxyindoles: Penoni, A.; Palmisano, G.; Broggini, G.; Kadowaki, A.; Nicholas, K. M. J. Org. Chem. 2006, 71, 823-825.
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note
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The lower selectivity may be due to the availability of only one ortho position on the nitroarene, but the lower conversion is likely due to a more difficult reduction of the nitroarene, which appears to be the slow step of the reaction (see also later). Due to the low yield of this indole, it could not be isolated in a pure form, and the identification of 3jb is to be considered only as a proposal.
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2 would consume only 0.66% of the starting nitroarene, making it impossible to detect its consumption.
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33646502405
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f values in a chromatographic separation. An analytically pure sample of 3cm could not be obtained, and accordingly, this compound is not mentioned in the tables or in the Experimental Section.
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27
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33646510904
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note
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28
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29
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33646497680
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note
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30 However, this difference is to be expected because Gladefter's study was conducted at 25 °C, whereas our reactions were performed at 170 °C. Because the nitroarene reduction becomes easier at higher temperatures, both ΔG and AAG values for different nitroarenes will decrease. This will accordingly affect the differences in rate constants and result in a lower slope in the Hammett plot.
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