✍ Scribed by Anne Rouchaud; William R. Kem
No coin nor oath required. For personal study only.
magnified image Anatabine is a major alkaloid in Nicotiana tabacum and its isomer, isoanatabine, was recently found in a marine worm. Reduction of 1‐methylpyridinium iodide with sodium borohydride gave 1‐methyl‐3‐piperideine, which was transformed with hydrogen peroxide into the N‐oxide. Reaction of the N‐oxide successively with trifluoroacetic anhydride and potassium cyanide gave 2‐cyano‐1‐methyl‐3‐piperideine. Its reaction with 3‐pyridylmagnesium chloride gave (±)‐__N‐__methyl‐isoanatabine. This was transformed with m‐chloroperbenzoic acid into the N‐oxide which was N‐demethylated with iron(II) sulfate, giving (±)‐isoanatabine. The successive applications of literature procedures for the N‐demethylation by decomposition of N‐oxide contributed to the knowledge of the mechanism of this oxidative rearrangement. On the other hand, the reduction of 1‐methylpyridinium iodide with sodium borohydride and with potassium cyanide present since the start of the reaction in a two layer ether‐water system, gave 2‐cyano‐1‐methyl‐4‐piperideine. This was transformed into (±)‐anatabine by the same sequence of reactions used for the synthesis of (±)‐isoanatabine. J. Heterocyclic Chem., (2010).
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