Issue 6, 2017

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
07 Mar 2017
Accepted
27 Mar 2017
First published
31 Mar 2017
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 4299-4305

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, 8, 4299 DOI: 10.1039/C7SC01042G

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements