L'acide hydroxylamine-O-sulfonique,réactif de choix pour la conversion d'aldéhydes en nitriles

Hydroxylamine-O-sulfonic acid: a convenient reagent for the conversion of aldehydes into nitriles . Hydroxylamine-O-sulfonic acid (HAS) proved to be an excellent reagent for the conversion of aliphatic, aromatic and heteroatomic aldehydes into nitriles. There, aldehydes in the form of suspension in HAS water solution, react rapidely to give the corresponding nitriles in high yield. Only with formylpyridines could the intermediate oxime-O-sulfonic acids be isolated.     

Acetohydroxamic acid: a new reagent for efficient synthesis of nitriles directly from aldehydes using Bi(OTf)3 as the catalyst

An efficient method for the preparation of nitriles directly from aldehydes by reaction with AHA using Bi(OTf)₃ as the catalyst is described. Bi(OTf)₃ is shown to be an efficient catalyst also for the conversion of aldoximes into nitriles.     

Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate

An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH₄OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.     

An efficient and convenient KF/Al2O3 mediated synthesis of nitriles from aldehydes

KF/Al₂O₃ brings about a facile one-pot and economical conversion of various aryl and alkyl aldehydes into the corresponding nitriles in high yields by reaction with hydroxylamine hydrochloride.     

Catalyst-free,efficient and one pot protocol for synthesis of nitriles from aldehydes using glycerol as green solvent

We described herein the novel, efficient and one-pot catalyst free protocol for the synthesis of nitriles from aldehydes by using hydroxyl amine hydrochlorides in glycerol as a green solvent. This protocol was efficiently used for transformation of aromatic aldehydes bearing electron-withdrawing and electron-donating groups into a aryl nitriles in good to excellent yields. The methodology offers a very simple, efficient and environmentally benign procedure.     

An efficient solvent free and one-pot conversion of aldehydes into nitriles using NH2OH.HCl/CH3COCl/charcoal system

The high yield conversion of aldehydes into their corresponding nitriles using hydroxylamine hydrochloride/ CH³COCl /charcoal system is presented. We have clearly shown the effectiveness of charcoal in these reactions.     

Synthesis of N-phenylpyrrole and pyrazole amidines and related diamines

N-Phenylpyrrole and pyrazole nitriles 3,4,10 were prepared in one step from the corresponding aldehydes. The nitriles were converted into novel amidines 5,6,14 and related diamines 7,8,12 were also prepared from the aldehydes. The orientation of the phenyl ring to the basic function was controlled by modifying the torsional angle between the rings by methyl group substitution on the heterocycle.     

Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat

A novel approach to convert aldehydes into nitriles using NH₃·H₂O/FeCl₂/NaI/Na₂S₂O₈ has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.     

Selective and facile synthesis of α,β-unsaturated nitriles and amides with N-hydroxyphthalimide as the nitrogen source

The direct conversion of α,β-unsaturated aldehydes to corresponding nitriles promoted by Pd(OAc)₂ and phthalic acid which was hydrolyzed from N-hydroxyphthalimide (NHPI) has been disclosed. Additionally, it was found that when water was used as the solvent, α,β-unsaturated amides was obtained as the main products in good to excellent yields. It was first reported that NHPI was utilized as the nitrogen source to synthesize α,β-unsaturated nitriles and amides from aldehydes. Control experiment demonstrated that aldehydes undergo a process of oximation and dehydration to form nitriles and amides.     

Catalyzed Addition of Aldehydes to Activated Double Bonds—A New Synthetic Approach

In the presence of cyanide ions as catalyst, aromatic and heterocyclic aldehydes can be smoothly added to α,β-unsaturated ketones, esters, and nitriles in aprotic solvents to form γ-diketones, 4-oxo carboxylic esters, and 4-oxo nitriles. Thiazolium salts in the presence of bases are also suitable catalysts; they permit not only addition of aromatic and heterocyclic aldehydes but also the addition of aliphatic aldehydes.     

Microwave Assisted,Solvent Free One Pot Synthesis of Nitriles from Aryl Aldehydes on Melamin Formaldehyde as Solid Support

Various aryl aldehydes underwent prompt one pot conversion into the corresponding nitriles in high yields by reacting with hydroxylamine hydrochloride supported on melamine formaldehyde under microwave irradiation in the presence of ammonium acetate as catalyst.     

Continuous-flow synthesis of nitriles from aldehydes via Schmidt reaction

Using continuous-flow synthesis of nitriles by Schmidt reaction, a variety of aldehydes could be smoothly transformed into the desired nitriles in good to excellent yields. The mild reaction conditions and the flowing reaction system greatly improved the safety and make the reaction easy to scale up.     

Efficient one pot synthesis of nitriles from aldehydes in solid state using peroxymonosulfate on alumina

In an environmentally benign solvent-free system, aldehydes are rapidly transformed into nitriles using peroxymonosulfate-alumina under microwave irradiation.     

Cost efficient synthesis of amides from oximes with indium or zinc catalysts

Simple indium and zinc salts have been successfully used as catalysts for the rearrangement of oximes into primary amides. The direct synthesis of nitriles or primary amides from aldehydes has also been demonstrated using these inexpensive catalysts.     

Innenrücktitelbild: Manganese‐Catalyzed Direct Nucleophilic C(sp2)?H Addition to Aldehydes and Nitriles (Angew. Chem. 46/2015)

Herein, a manganese‐catalyzed nucleophilic addition of inert C(sp²) H bonds to aldehydes and nitriles is disclosed by virtue of a dual activation strategy. The reactions feature mild reaction conditions, excellent regio‐ and stereoselectivity, and a wide substrate scope, which includes both aromatic and olefinic C H bonds, as well as a large variety of aldehydes and nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles.     

Manganese‐Catalyzed Direct Nucleophilic C(sp2)H Addition to Aldehydes and Nitriles

Herein, a manganese‐catalyzed nucleophilic addition of inert C(sp²)? H bonds to aldehydes and nitriles is disclosed by virtue of a dual activation strategy. The reactions feature mild reaction conditions, excellent regio‐ and stereoselectivity, and a wide substrate scope, which includes both aromatic and olefinic C? H bonds, as well as a large variety of aldehydes and nitriles. Moreover, mechanistic studies shed light on possible catalytic cycles.     

Direct Synthesis of Nitriles from Aldehydes Using Chloramine-T/KI in Aqueous Ammonia

A convenient method for direct conversion of aldehydes into nitriles has been developed using chloramine-T/KI in aqueous ammonia.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource: Full experimental and spectral details.]     

Reductive Amination of Carbonyl Compounds with Ammonia and Hydrogenation of Nitriles to Primary Amines with Heterogeneous Cobalt Catalysts

Reductive amination of aldehydes/ketones with aqueous NH3 and hydrogenation of nitriles to primary amines with Co catalysts were reported. Co@NC-700 exhibited remarkable activity and high selectivity for the reductive amination of aldehydes/ketones with aqueous NH3 and the hydrogenation of nitriles to primary amines. Several primary amines can be obtained with good to excellent yields via the reductive amination of aldehydes/ketones and the hydrogenation of nitriles. The nitrogen-doped carbon(C)-supported Co@NC-700 metal catalyst was prepared via the pyrolysis of bioMOF Co/adenine in activated C. Co@NC-700 can be reused five times without evident loss of activity.     

A one-step transformation of aromatic aldehydes to nitriles,using S,S-Dimethylsulfurdiimide as iminating agent. Isolation of dithiatetrazocines as reaction intermediates.

$\text{S}$,$\text{S}$-Dimethylsulfurdiimide is explored as a novel and effective reagent for the direct synthesis of aromatic nitriles from aldehydes. A novel eight-membered heterocycle is isolated as a reaction intermediate and a mechanism for this reaction is discussed.     

Synthetic application of in situ generation of N-acyliminium ions from α-amido p-tolylsulfones for the synthesis of α-amino nitriles

In the presence of catalytic amount of bismuth bromide (5 mol %) the α-amido p-tolylsulfones are converted into N-acyliminium ions, which undergo the nucleophilic addition of trimethylsilyl cyanide (TMSCN) to provide the N-protected α-amino nitriles in very good yield. A variety of α-amido p-tolylsulfones were prepared from aromatic as well as aliphatic aldehydes for the synthesis of α-amino nitriles.