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Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Synthesis of Azocanes from Piperidines via an Azetidinium Intermediate
Malte Leverenz1, Guillaume Masson1, Domingo Gomez Pardo1
1Molecular, Macromolecular Chemistry and Materials, UMR 7167 ESPCI Paris, CNRS, PSL University, 10 rue Vauquelin, 75231, Paris Cedex 05, France.
Abstract:
α-Trifluoromethyl azocanes are accessible from 2-(trifluoropropan-2-ol) piperidines by metal-free ring-expansion involving a bicyclic azetidinium intermediate. The opening of the azetidinium intermediate was achieved by various nucleophiles (amines, alcoholates, carboxylates, phosphonates, halides and pseudo-halides) with an excellent regio- diastereo- and enantioselectivity and in good yields. The relative configuration of the piperidines and azocanes were assigned and the deprotected azocanes offer opportunities for further derivatization.
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