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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Highly enantioselective syntheses of heterocycles via intramolecular Ir-catalyzed allylic amination and
Carolin Welter1, Axel Dahnz, Bernhard Brunner
1Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, D-69120 Heidelberg, Germany.
Abstract:
[reaction: see text] Enantioselective Ir-catalyzed intramolecular allylic aminations and etherifications are described. Up to 97% ee was achieved using catalysts prepared by in situ activation of mixtures of phosphorus amidites and [Ir(COD)Cl]2. Sequential aminations of bis-allylic carbonates, involving an inter- followed by an intramolecular reaction, gave trans-N-benzyl-2,5-divinylpyrrolidine and trans-N-benzyl-2,6-divinylpiperidine with > or = 99% ee. New phosphorus amidites as well as improved conditions for intermolecular aminations are reported.
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