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Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C–N bond formation

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Abstract

We have identified an enantioselective copper-catalyzed O-to-N formal [1,3]-rearrangement to form N-propargylic-2-pyridones. This enantioconvergent O-to-N propargylic rearrangement occurs rapidly at ambient temperature and high enantioselectivity is observed for a range of 3-alkyl-substituted substrates. Stereochemical features include a mild kinetic enantioenrichment of the substrate and a non-linear relationship between product and ligand enantiopurity. Based on kinetic analyses and cross-over experiments, we put forward a mechanistic proposal involving Cu-acetylides as well as bimetallic intermediates in which coordination to the pyridyl nitrogen is likely a crucial binding interaction.

Graphical abstract: Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C–N bond formation

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Publication details

The article was received on 07 Mar 2017, accepted on 27 Mar 2017 and first published on 31 Mar 2017


Article type: Edge Article
DOI: 10.1039/C7SC01042G
Citation: Chem. Sci., 2017, Advance Article
  • Open access: Creative Commons BY license
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    Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C–N bond formation

    L. Cheng, A. P. N. Brown and C. J. Cordier, Chem. Sci., 2017, Advance Article , DOI: 10.1039/C7SC01042G

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