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21
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2442477253
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note
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3CN.
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22
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2442571817
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note
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All the catalysts were completely soluble in AcOEtYdioxane 1:1 except for 1g which was thus not used. in the kinetic studies.
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23
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2442540046
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note
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+) proposed by Arnold and his associates.19
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25
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2442590538
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note
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A ρ value (-0.69) very close to that here reported was determined by Minisci et al. for the aerobic oxidation of benzylic alcohols by the unsubstituted NHPI.10)
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26
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0037134157
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Minisci, F.; Punta, C.; Recupero, F.; Fontana, F.; Pedulli, G. F. J. Org. Chem. 2002, 67, 2671.
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Minisci, F.1
Punta, C.2
Recupero, F.3
Fontana, F.4
Pedulli, G.F.5
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27
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2442626410
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note
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23 an increase of the KIE should be expected by decreasing the O-H BDE of the aryl substituted NHPI, i.e., by introducing electron-donating substituents.
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28
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0038201600
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Nobuyoshi, K.; Cai, Y.; Espenson, J. H. J. Phys. Chem. A 2003, 107, 4262.
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Nobuyoshi, K.1
Cai, Y.2
Espenson, J.H.3
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29
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0344391968
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Such a high isotope effect value was interpreted as due to quantum mechanical.tunneling taking part in the benzylic HAT from the alcohol to the PINO. Nobuyoshi, K.; Saha, B.; Espenson, J. H. J. Org. Chem. 2003, 68; 9364.
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Nobuyoshi, K.1
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30
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2442448129
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note
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Rate-determining hydrogen atom abstraction from C-H bonds by PINO (Scheme 1, path b) in aerobic oxidations catalyzed by NHPI is well documented.3,9-11 The possibility of a rate-determining formation of aryl-substituted PINO (Scheme 1, path d) should be considered if a higher alcohol/X-NHPI molar ratio is used.14.
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31
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2442609519
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note
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2 system.
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32
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2442425075
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note
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. + ρσ+) proposed by Arnold.TM
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33
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33947482041
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Walling, C.; Rieger, A. L.; Tanner, D. D. J. Am. Chem. Soc. 1963, 85, 3129.
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36
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2442594802
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note
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2 groups could be also explained by an electron transfer mechanism from the alcohol to the X-PINO. We have excluded this possibility by the fact that the oxidation of the mechanistic probe 1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanol led to the formation of 1-(3,4-dimethoxyphenyl)-2,2-dimethyl-1-propanone as the only reaction product and no traces of 3,4-dimethoxybenzaldehyde have been detected (see the Experimental Section).30
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0002715207
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