Jump to main content
Jump to site search

Issue 16, 2019

Asymmetric diastereodivergent Michael addition of 2-chloromalonate esters to conjugated imines enabled by catalyst metal change

Author affiliations

Abstract

Despite recent progress in asymmetric diastereodivergent reactions leading to products bearing two stereogenic centers, little research has been devoted to processes were a stereogenic center and a double bond are formed. Here, we report the asymmetric diastereodivergent Michael addition of 2-chloromalonate esters to N-tosyl β,γ-unsaturated α-ketimino esters to give chiral α,β-dehydro-α-aminoesters bearing either a Z or E enamine moiety, using pyBOX-metal complexes. Diastereodivergency is achieved by simply changing the metal ion from a trivalent La(III) to a divalent Ca(II) ion, providing the Z or E enamines. Computational studies reveal the crucial role of London interactions between the aromatic residues on the imine and the pyBOX ligand, which are conditioned by the different coordination modes of La(III) and Ca(II), in the change of selectivity depending on the used metal.

Graphical abstract: Asymmetric diastereodivergent Michael addition of 2-chloromalonate esters to conjugated imines enabled by catalyst metal change

Supplementary files

Article information


Submitted
07 Jun 2019
Accepted
02 Jul 2019
First published
03 Jul 2019

Org. Chem. Front., 2019,6, 2907-2915
Article type
Research Article

Asymmetric diastereodivergent Michael addition of 2-chloromalonate esters to conjugated imines enabled by catalyst metal change

M. Espinosa, G. Blay, L. Cardona, P. Merino and J. R. Pedro, Org. Chem. Front., 2019, 6, 2907 DOI: 10.1039/C9QO00741E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements