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DFT calculations also suggest that the one-electron oxidation of azepines (4 n - 1 state) gives rise to a slight expansion toward a planar conformation, the degree of which is smaller than that of two -electron oxidation (4 n - 2 state). This conformational change is probably due to the delocalization of the charge generated, not the aromatic stabilization, and seems to be true for most 4 n -electron conjugated cyclic systems, including thiepins and [8]annulenes. Similar geometric rearrangements are found to occur as well in simple N-functionalized 3-aminothiophenes. See
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3P, and switching to the BINAP ligand furnished the desired N -benzylazepine 4d. However, the yield was low presumably due to reduced reactivity of the first amination product. It appears that while the bidentate ligands successfully suppress the undesired β-hydride elimination, the catalyst complex is not active enough for the cyclization step (the second amination)
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3P, and switching to the BINAP ligand furnished the desired N -benzylazepine 4d. However, the yield was low presumably due to reduced reactivity of the first amination product. It appears that while the bidentate ligands successfully suppress the undesired β-hydride elimination, the catalyst complex is not active enough for the cyclization step (the second amination).
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The oxidation potential of nitrogen-substituted thiophenes has been shown to be very sensitive to changes in nitrogen substitution. See ref 36
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