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

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 s...

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Published inChemical science (Cambridge) Vol. 8; no. 6; pp. 4299 - 4305
Main Authors Cheng, Li-Jie, Brown, Alexander P. N., Cordier, Christopher J.
Format Journal Article
LanguageEnglish
Published CAMBRIDGE Royal Soc Chemistry 2017
Royal Society of Chemistry
Subjects
Ambient temperature
Bimetals
Binding
Bonding
Chemistry
Chemistry, Multidisciplinary
Ligands
Migration
Nitrogen
Physical Sciences
Science & Technology
Substrates
AMINATION
BETA-KETOESTERS
ALLYLIC TRANSPOSITION
2-PYRIDONES
ALKYLATION
ESTERS
SIGMATROPIC REARRANGEMENT
DERIVATIVES
3+2 CYCLOADDITION
ALLENYLIDENE
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Summary: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.
Bibliography:UKRI
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ISSN:2041-6520
2041-6539
DOI:10.1039/C7SC01042G