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Intramolecular Cyclization Manifolds of 4‑Alkylpyridines Bearing Ambiphilic Side Chains: Construction of Spirodihydropyridines or Benzylic Cyclization via Anhydrobase Intermediates

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journal contribution
posted on 21.09.2012, 00:00 by Sharavathi G. Parameswarappa, F. Christopher Pigge
4-Alkylpyridines possessing nucleophilic β-dicarbonyl side chains have been converted to spirodihydropyridines upon treatment with ethyl chloroformate and sub-stoichiometric amounts of Ti­(OiPr)4. Alternatively, inclusion of mild base in the reaction medium was found to facilitate generation of anhydrobase intermediates. Subsequent aldol-like condensations with electrophilic side chain moieties followed by hydrolysis delivered benzylically cyclized pyridines in good yield. In situ hydrogenation of cyclized anhydrobase intermediates afforded 4-substituted piperidines.