Enantioselective propargylic [1,3]-rearrangements: copper-catalyzed O-to-N migrations toward C-N bond formation
File(s)
Published version
Author(s)
Cheng, L-J
Brown, APN
Cordier, CJ
Type
Journal Article
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.
Date Issued
2017-03-31
Date Acceptance
2017-03-27
Citation
CHEMICAL SCIENCE, 2017, 8 (6), pp.4299-4305
ISSN
2041-6520
Publisher
Royal Society of Chemistry
Start Page
4299
End Page
4305
Journal / Book Title
CHEMICAL SCIENCE
Volume
8
Issue
6
Copyright Statement
© 2017 The Royal Society of Chemistry. This article is licensed under a
Creative Commons Attribution 3.0 Unported Licence (https://creativecommons.org/licenses/by/3.0/).
Creative Commons Attribution 3.0 Unported Licence (https://creativecommons.org/licenses/by/3.0/).
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000402384900016&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
BETA-KETOESTERS
ALLYLIC AMINES
SIGMATROPIC REARRANGEMENT
SUBSTITUTION-REACTIONS
ASYMMETRIC CATALYSIS
3+2 CYCLOADDITION
ALKYL MIGRATION
ESTERS
2-PYRIDONES
AMINATION
Publication Status
Published