Heterogeneously Catalyzed Oxidative Cyanation of Tertiary Amines with Sodium Cyanide/Hydrogen Peroxide using Polymer‐Supported Iron(II) Phthalocyanines as Catalyst

Abstract

The first report on heterogeneously catalyzed oxidative cyanation of various tertiary amines to the corresponding a-amino nitriles with high yields and selectivity by using hydrogen peroxide oxidant in presence of sodium cyanide and Fe(II) phthalocyanine supported on a polymer as catalyst is described. The present method has the added benefits of facile recovery of the catalyst from the reaction mixture and its subsequent use without further activation. Consistent catalytic activity with no metal leaching was observed during this course.

Magnetic graphitic carbon nitride: its application in the C–H activation of amines

“…[10][11][12][13][14] The catalytic variant of these reagents has lately been emphasized via C-H activation of amines using transition metal catalysts. [15][16][17][18] Although the catalytic methods have abetted in reducing the waste generation, the homogeneous nature of the catalyst does not allow recycling and reuse of the reagents; waste generated, even in catalytic systems, becomes prominent on large scale industrial use. Consequently, research shave realized that the use of heterogeneous systems is the way forward to address the environmental issues that diminish the toxic waste generation.…”

“…The plausible mechanism of the reaction entails the formation of reactive oxo-Iron(IV) species which upon its reaction with tertiary amine results in the formation of iminium ion; [35][36] this intermediate reacts with in-situ generated HCN providing the desired α-aminonitrile (Figure 3). 37 …”

PEGylated magnetic nanoparticles (PEG@Fe 3 O 4 ) as cost effective alternative for oxidative cyanation of tertiary amines via C H activation

“…In continuation to our efforts towards developing efficient and cost-effective methodologies for organic transformations [39][40][41], herein we report a facile, highly efficient and selective method for the oxidative cyanation of tertiary amines via C H bond activation using PEGylated magnetic nanoparticles as catalyst in the presence of hydrogen peroxide as oxidant and NaCN in acetic acid as a cyanide source (Scheme 1). Furthermore, facile recovery of the catalyst with the use of an external magnet makes the developed method attractive for wider applications.…”

Acetone Cyanohydrin: A Convenient Alternative of Toxic Sodium Cyanide/Acetic Acid for Oxidative Cyanation of Tertiary Amines

“…The classic method known as Strecker reaction [6] involving the one pot condensation of a carbonyl compound, an amine and cyanide in presence of homogeneous [7][8][9] or heterogeneous [10][11][12][13] catalysts is well documented albeit provide poor product yields. Alternatively, the oxidation of tertiary amines with stoichiometric oxidants such as chlorine dioxide [14], m-chloroperbenzoic acid [14,15], hydrogen peroxide [16,17] or mercuric acetate [18], followed by the reaction of the iminium intermediate by cyanide ion represents a simple approach for their synthesis. However, the use of stoichiometric oxidants and production of huge amounts of hazardous waste is undesirable from environmental viewpoints.…”