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5929001 
Journal Article 
Template catalysis by manganese pincer complexes: oxa- and aza-Michael additions to unsaturated nitriles 
Tang, S; Milstein, D 
2019 
Chemical Science
ISSN: 2041-6520
EISSN: 2041-6539 
10 
39 
8990-8994 
English 
31762979 
WOS:000489761300006 
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.