Issue 39, 2019

Template catalysis by manganese pincer complexes: oxa- and aza-Michael additions to unsaturated nitriles

Abstract

Activation of C[triple bond, length as m-dash]N bonds by metal–ligand cooperation provides a new route for the functionalization of nitriles. Herein, we report the electrophilic activation of unsaturated nitriles by dearomatized manganese pincer complexes for the oxa- and aza-Michael addition reactions under very mild and neutral conditions. Derivatives of acrylonitrile and allyl cyanide furnished the corresponding β-addition products by reacting with alcohols and amines. Mechanistically, the catalysis is mostly ligand based. Reaction of the dearomatized PNN–Mn complex with 2-pentenenitrile or 3-pentenenitrile furnished an enamido–Mn complex. The equilibrium between an enamido complex and a ketimido complex, and reversible C–C bond formation with the ligand are proposed to play central roles in the catalysis.

Graphical abstract: Template catalysis by manganese pincer complexes: oxa- and aza-Michael additions to unsaturated nitriles

Supplementary files

Article information

Article type
Edge Article
Submitted
03 Jul 2019
Accepted
07 Aug 2019
First published
07 Aug 2019
This article is Open Access

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

Chem. Sci., 2019,10, 8990-8994

Template catalysis by manganese pincer complexes: oxa- and aza-Michael additions to unsaturated nitriles

S. Tang and D. Milstein, Chem. Sci., 2019, 10, 8990 DOI: 10.1039/C9SC03269J

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