Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(<scp>ii</scp>) complexes

Borau‐Garcia, Javier; Gutsulyak, Dmitry V.; Burford, Richard J.; Piers, Warren E.

doi:10.1039/c4dt03902e

Cited by 55 publications

(37 citation statements)

References 18 publications

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“…10 Thus, during various silylation processes there is a potential risk of byproduct formation when there is a nitrile-containing functionality in the substrate or acetonitrile as solvent. Table 1 Synthetic Methods for Converting Nitriles into Amides 5,7,[10][11][12][13][14][15][16][17] Conversion of acetonitrile into acetamide has also been accomplished using catalysts based on ruthenium, 11,[18][19][20] nickel, 21,22 cobalt, 12 platinum, 23,24 palladium, 14,25 osmium, 15,26 gold, 27 silver, 17,28 and copper. 16,29 Manganese dioxide based systems have also been applied.…”

Section: Review Syn Thesis 2 Fundamental Reactions With Acetonitrile mentioning

confidence: 99%

Acetonitrile as a Building Block and Reactant

Hoff

2018

Synthesis

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Acetonitrile is popular as a solvent for performing organic reactions, as a ligand in inorganic chemistry, as a mobile phase in chromatography, and as an electrolyte solvent in dye-sensitized solar cells. This is mainly due to its ability to dissolve both polar and nonpolar components. However, acetonitrile is also a valuable building block allowing atom-efficient transformations in synthetic organic chemistry. The aim of this review is to highlight synthetic transformations using acetonitrile, covering both classical approaches and modern strategies proceeding through radical intermediates or mediated by metal catalysis. Besides showcasing synthetic protocols useful for acetonitrile and analogues, warnings for when not to use acetonitrile as a solvent are also provided.1 Introduction2 Fundamental Reactions with Acetonitrile3 Cyanomethylation of Non-Aromatics4 The Acetonitrile Nitrogen as a Nucleophile5 The Blaise Reaction6 Synthesis of Pyridines7 Other Cyclization Reactions8 Cyanomethylation of Arenes and Heteroarenes9 Acetylation of Arenes Using Acetonitrile10 Synthesis of N-Arylacetamides11 Cyanation Using Acetonitrile as a Cyanide Source12 When To Avoid Acetonitrile as a Solvent13 Conclusion

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Section: Review Syn Thesis 2 Fundamental Reactions With Acetonitrile mentioning

confidence: 99%

Acetonitrile as a Building Block and Reactant

Hoff

2018

Synthesis

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“…As au seful intermediate, [1] the nitrilemoiety is one of the most important functional groups [2] andc an be easily converted into corresponding amines, [3] amides, [4] ketones, [5] carboxylic acids [6] and esters. [7] Furthermore,i ti sa lso ak ey motif in numerous useful compounds such as bioactive natural products, [8] pharmaceuticals, [9] and functional materials.…”

Section: Introductionmentioning

confidence: 99%

A Mild TEMPO‐Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles

Fang

et al. 2016

Adv Synth Catal

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An efficient method to prepare nitriles from aldehydesu sing hexamethyldisilazane (HMDS) as the nitrogen source hasb een developed. Ther eactions were performed with 2,2,6,6-tetramethylpiperidine l-oxyl (TEMPO) as the catalyst, NaNO 2 or TBN as the co-catalyst, andm olecular oxygena st he terminal oxidant under mild conditions.Avariety of aromatic, heteroaromatic, aliphatic anda llylica ldehydes could be converted into their corresponding nitriles in good to excellent yields.

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“…In addition to fundamental metal--centred processes like oxidative addition 1, 2 or sigma bond metathesis, 3 activation of bonds through metal--ligand cooperation has emerged as an additional tool for challenging bond cleavages. 4 Numerous design principles exist for ligands capable of participating in cooperative substrate activation, 4--9 including pincer--supported pyridine rings prone to undergo dearomatization-aromatization, ligands containing a basic amide functionality able to accept electrophiles, and the incorporation of a reactive carbene moiety in the ligand scaffold, (Chart 1); these species are competent in the activation of a wide variety of substrates via metal--ligand cooperation between the nickel center and the nucleophilic and basic carbene carbon, 12,14,15 as are closely related palladium complexes. 16--19 Inspired by reports of the accessibility of formally oxidized palladium carbenes III and IV, systems containing electrophilic and radical carbene fragments, respectively, through redox chemistry in analogous PC carbene P palladium complexes, 20 we sought to access related nickel complexes through more direct synthetic routes.…”

Section: Introductionmentioning

confidence: 99%

Redox–state Dependent Activation of Silanes and Ammonia with Reverse Polarity (PCcarbeneP)Ni Complexes: Electrophilic vs. Nucleophilic Carbenes

Piers¹,

LaPierre²,

Gendy³

2018

Preprint

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A rigidified PCalkylP ligand allowed for the synthesis and charactarization of cationic and radical PCCarbeneP nickel complexes in which the carbene anchor of the pincer framework is electrophilic rather than nucleophilic. Alpha-hydride abstraction from (PCalkylP)nickel halide complex readily leads to the cationic carbene complex, which furnishes the radical carbene complex by one electron reduction. The reactivity of these reverse polarity carbene complexes towards small molecules (H2, CO, CO2, R3SiH, NH3) reveals different modes of activation when compared to previously reported nucleophilic nickel carbene complexes, and a clear dependence on the redox state of the complex. For H2, CO and CO2, no reaction is observed, but silanes react via hydride transfer and formation of solvated silylium ions. Ammonia is activated in a novel way, wherein it coordinates the carbene carbon and is deprotonated to form a robust C-N bond. This is not only a rare example of ammonia activation by a first row transition metal but also evidence of the intermediacy of group 10 carbenes in direct C-N bond forming reactions.

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Selective hydration of nitriles to amides catalysed by PCP pincer supported nickel(ii) complexes

Cited by 55 publications

References 18 publications

Acetonitrile as a Building Block and Reactant

Acetonitrile as a Building Block and Reactant

A Mild TEMPO‐Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles

Redox–state Dependent Activation of Silanes and Ammonia with Reverse Polarity (PCcarbeneP)Ni Complexes: Electrophilic vs. Nucleophilic Carbenes

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