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dependencies of yield and selectivity on the reagent amount have been studied in detail on the example of the synthesis of pyridine 2a. If copper II was applied stoichiometrically 3 mol per mol aldimine only 39% of 2a was obtained but 8% of the corresponding imidazo1, 5-a-pyridine was found as a by-product. If the amount of of Cu II was enhanced to 4 equivalents per mol aldimine the yield of 2a increased to 53% and only 2% of the imidazo1, 5-a-pyridine was obtained. If an even higher excess of Cu II was applied the yield of 2a decreased again. However, the yield of 2a was moderate at all reagent concentratioms owing to the formation of several other side products. as a characteristic by-product of this reaction the corresponding ketone 1-acetylpyridine was isolated. Its formation can be explained by an oxidative scission of the aldimine
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The dependencies of yield and selectivity on the reagent amount have been studied in detail on the example of the synthesis of pyridine (2a). If copper (II) was applied stoichiometrically (3 mol per mol aldimine) only 39% of (2a) was obtained but 8% of the corresponding imidazo[1, 5-a]-pyridine was found as a by-product. If the amount of of Cu (II) was enhanced to 4 equivalents per mol aldimine the yield of (2a) increased to 53% and only 2% of the imidazo[1, 5-a]-pyridine was obtained. If an even higher excess of Cu (II) was applied the yield of (2a) decreased again. However, the yield of (2a) was moderate at all reagent concentratioms owing to the formation of several other side products. as a characteristic by-product of this reaction the corresponding ketone (1-acetylpyridine) was isolated. Its formation can be explained by an oxidative scission of the aldimine.
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A plausible alternative to the stepwise mechanism to give this intermediate is a concerted mechanism 1, 3-dipolar cycloaddition
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A plausible alternative to the stepwise mechanism to give this intermediate is a concerted mechanism (1, 3-dipolar cycloaddition).
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