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

Shan Tang, David Milstein

Research output: Contribution to journalArticle

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Abstract

Activation of CN 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.

Original languageEnglish
Pages (from-to)8990-8994
Number of pages5
JournalChemical Science
Volume10
Issue number39
DOIs
Publication statusPublished - Jan 1 2019

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Nitriles
Manganese
Catalysis
Ligands
Chemical activation
Acrylonitrile
Addition reactions
Amines
Metals
Alcohols
Derivatives

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Template catalysis by manganese pincer complexes : Oxa- and aza-Michael additions to unsaturated nitriles. / Tang, Shan; Milstein, David.

In: Chemical Science, Vol. 10, No. 39, 01.01.2019, p. 8990-8994.

Research output: Contribution to journalArticle

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