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Triethylamine was used instead of collidine because of little difference in the selectivities
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38
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85030817740
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note
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The N-isobutyryl form of 1a is in equilibrium with 1a, in addition, the chemical shifts of the pyridinium protons receive an anisotropic effect from the N-acyl carbonyl group. Therefore, N-methylpyridinium salt 5 was used instead of N-isobutyryl form of 1a to neglect such inadequate effects for evaluation of the intramolecular interaction
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39
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85030814168
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note
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NOE experiments of N-isobutyryl form of 1a clarified that the N-acyl carbonyl oxygen is close to H6. Irradiation of H2 and H6 resulted in 17.6% and 0.5% NOEs for COCH proton, respectively
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40
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85030810193
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note
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DFT calculations at the B3LYP/6-31G* level suggested that conformer A where the CS group blocks the A-side of the pyridinium is 1.02 kcal/mol more stable than conformer B
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41
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37049090349
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