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20844454838
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note
-
From the initial ΔOD we can estimate that the PINO concentration is about 0.03 mM.
-
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39
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-
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note
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2 = 0.997), that probably indicates that the partial positive charge in the transition state should be mainly localized on the nitrogen atom and not on the aromatic ring.
-
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41
-
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20844432618
-
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note
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Secondary isotope effects are likely obscured by the error limit.
-
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42
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note
-
Of course, substituents also influence the rate of the second step. However, the effect on the electron-transfer step should be much more important, as also shown by the observed electronic effects of the substituents.
-
-
-
-
44
-
-
20844451657
-
-
note
-
Actually, for this reaction Watanabe et al. assumed that the radical cation undergoes a hydrogen atom transfer and not a proton-transfer reaction. At present, we cannot exclude that such a possibility occurs also in our case, the radical cation reacting with PINO to form an a-amino carbocation that can either be converted into the carbinolamine or react with the N-hydroxyphthalimide anion, produced in step a, to give the adduct (Scheme 1).
-
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47
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20844461753
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note
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ΔG°′ values and the details of their calculation are reported in the Supporting Information.
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Arulmozhiraja, S.1
Sato, T.2
Yabe, A.3
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