Hydroxylamine on Clay: a Direct Synthesis of Nitriles from Aromatic Aldehydes Using Microwaves Under Solvent-Free Conditions

In a solvent-free system, hydroxylamine hydrochloride impregnated montmorillonite K 10 clay expeditiously converts arylaldehydes to the corresponding nitriles under microwave irradiation conditions. This rapid one-pot method produces pure products in high yields (89–95%) within 1 to 1.5 min.     

Ionic liquid-induced conversion of methoxymethyl-protected alcohols into nitriles and iodides using [Hmim][NO3]

This Letter reports a one-pot efficient conversion of methoxymethyl-ethers into their corresponding nitriles and iodides using the ionic liquid, 1-methyl-3H-imidazolium nitrate ([Hmim][NO₃]) under microwave irradiation. A variety of products were prepared in high yields using this method.     

One-pot cyclization of dilithiated nitriles with isothiocyanates and epibromohydrin. Synthesis of 2-cyano-1-(hydroxymethyl)cyclopropanes and 2-cyanomethylidene-4-(hydroxymethyl)thiazolidines

The cyclization of dilithiated nitriles with epibromohydrin afforded 2-cyano-1-(hydroxymethyl)cyclopropanes. 2-Cyanomethylidene-(4-hydroxymethyl)thiazolidines were prepared by one-pot cyclization of dilithiated nitriles with isothiocyanates and epibromohydrin.     

An expeditious procedure for the synthesis of purines from aminoimidazolecarbaldehydes

Reactions of 4-amino-1,2-dimethylimidazole-5-carbaldehyde ( 1 ) and 5-amino-1-methylimidazole-4-car-baldehydes 3 with nitriles, in the presence of dry hydrogen chloride afforded to the formation of purine derivatives. This constitutes a facile and versatile one-pot synthesis of purines. The use of formamide instead of nitriles leads to the respective purines without substituents on the pyrimidine ring, 2d and 4e,f .     

One-Pot Synthesis of 3,5-Disubstituted 1,2,4-Oxadiazoles Directly from Nitrile and Hydroxylamine Hydrochloride Under Solvent-Free Conditions Using Potassium Fluoride as Catalyst and Solid Support

A one-pot synthesis of 3,5-disubstituted 1,2,4-oxadiazoles with two identical substituents directly from the reaction of nitriles and hydroxylamine hydrochloride in the presence of potassium fluoride as catalyst and solid support under solvent-free condition is described. Moreover, the formation of products has been discussed, and a plausible mechanism has been presented. Simplicity of the process, workup in aqueous media, and excellent yields are some advantages of this method.     

Metal triflate catalyzed reactions of alkenes, NBS, nitriles, and TMSN3: synthesis of 1,5-disubstituted tetrazoles

A versatile and highly efficient protocol for the synthesis of 1,5-disubstituted tetrazoles has been developed by metal triflate catalyzed one-pot reaction of alkenes, NBS, nitriles, and TMSN3. Among the metal triflates, Zn(OTf)2 was found to be the best catalyst. Use of different combinations of alkenes and nitriles generate a variety of 1,5-disubstituted tetrazoles containing an additional alpha-bromo functionality of the N1-alkyl substituent.     

Chiral bisformamides as effective organocatalysts for the asymmetric one-pot, three-component strecker reaction

C2-symmetric chiral bisformamides have been shown to catalyze the asymmetric one-pot, three-component Strecker reaction, which produced the alpha-amino nitriles in excellent yields (up to 99%) with good enantioselectivities (up to 86% ee). Optically pure products could be obtained after a single recrystallization. A possible transition state (TS 1) has been proposed to explain the origin of asymmetric inductivity and reactivity according to the geometry of catalyst 2a optimized at the B3LYP/6-31G(d) level and the absolute configuration of product 4a.     

Synthesis of Ketones with Alkyl Phosphonates and Nitriles as Acyl Cation Equivalent: Application of Dephosphonylation Reaction of β-Functionalized Phosphonate with Hydride

The preparation of several α-substituted ketones is performed in a one-pot procedure with alkyl phosphonates and aromatic nitriles by subsequent treatment of LiAlH₄. A new method for nitriles used as an acyl cation equivalent is described.     

Zinc Chloride–Catalyzed Expeditious Route to Nitriles

Zinc chloride has been found to be an excellent catalyst for a one-pot synthesis of nitriles from araldehydes and hydroxylammonium chloride under solvent-free conditions. The features of the present method are short reaction time, easy workup procedure, and good yields of the nitriles.     

Ultrasound-promoted synthesis of nitriles from aldoximes under ambient conditions

Copper(II) acetate proves to be an active catalyst for ultrasound-promoted conversion of aldoximes into nitriles. This dehydration reaction was carried out in acetonitrile under ambient conditions to provide nitriles with moderate tolerance toward water, which allows one-pot synthesis of a nitrile from an aldehyde with minimal purification.     

Clean one-pot synthesis of 1,2,4-oxadiazoles under solvent-free conditions using microwave irradiation and potassium fluoride as catalyst and solid support

Potassium fluoride was found to be an efficient catalyst and solid support for the synthesis of 3,5-disubstituted-1,2,4-oxadiazoles. In this work, a one-pot method for the synthesis of these compounds from the reaction of nitriles with hydroxylamine hydrochloride and acyl chloride in the presence of potassium fluoride under solvent-free conditions using microwave irradiation has been developed. The advantages of using potassium fluoride as a solid support in comparison to conventional solid supports are simple operation and convenient separation of the products.     

Synthesis of β-hydroxy nitriles and 1,3-amino alcohols from epoxides using acetone cyanohydrin as a LiCN precursor

The reaction of acetone cyanohydrin with MeLi affords a LiCN·acetone complex that can be made to react with epoxides in THF, either in one-pot or using isolated samples of the cyanide complex, to cleanly afford β-hydroxy nitriles upon aqueous workup; in situ hydride reduction of nitriles affords 1,3-amino alcohols.     

A synthetic approach to azetidinones from nitriles and lithiumtriethoxyaluminium hydride.

A convenient one-pot process for direct conversion of nitriles to 3,4-disubstituted azetidinones has been developed.     

An efficient and scalable one-pot double Michael addition-Dieckmann condensation for the synthesis of 4,4-disubstituted cyclohexane beta-keto esters

A simple, scalable, and efficient one-pot methodology for the synthesis of 4,4-disubstituted cyclohexane beta-keto esters from benzylic nitriles or esters and methyl acrylate promoted by potassium tert-butoxide is described. The process relies on a tandem double Michael addition-Dieckmann condensation reaction, which results in the formation of three discrete carbon-carbon bonds in a single pot, including a quaternary center. The method allows for the convenient and rapid synthesis of a variety of 4-aryl-4-cyano-2-carbomethoxycyclohexanone and 4-aryl-2,4-biscarbomethoxycyclohexanone building blocks for use in natural products synthesis and medicinal chemistry.     

Magnesia-supported hydroxylamine hydrochloride in the presence of sodium carbonate as an efficient reagent for the synthesis of 1,2,4-oxadiazoles from nitriles

An efficient one-pot method has been developed for the synthesis of 1,2,4-oxadiazoles through a one-pot reaction of nitriles with hydroxylamine hydrochloride in the presence of magnesia-supported sodium carbonate followed by reaction with acyl halides under solvent-free conditions using microwave irradiation. This method is easy, rapid and good yielding.     

Rapid microwave-assisted solution phase synthesis of substituted 2-pyridone libraries

2-Pyridone and 2-quinolone analogues are well-known biologically active heterocyclic scaffolds. Libraries of 3,5,6-substituted 2-pyridone derivatives are generated by rapid microwave assisted solution phase methods using a one-pot, two-step protocol. The three-component condensation of CH-acidic carbonyl compounds, N,N-dimethylformamide dimethylacetal and methylene active nitriles, leads to 2-pyridones and fused analogues in moderate to good overall yields and high purities. The proposed mechanism of this novel multi-component reaction, structure elucidation of products and intermediates are discussed.     

Reaction of silyldihalomethyllithiums with nitriles: formation of alpha-keto acylsilanes via azirines and 1,3-rearrangement of silyl group from C to N

A synthesis of alpha-keto acylsilanes, where 2-bromo-2H-azirine participates as a key intermediate, is reported. The reaction of silyldibromomethyllithium with aryl nitriles provides alpha-keto acylsilanes in good yields. Interestingly, silyldichloromethyllithium induces aza-1,3-Brook rearrangement of the silyl group in th reaction with nitriles. The rearrangement enables a three-component coupling reaction in a one-pot operation.     

Facile transformation of esters to nitriles

Various esters were efficiently converted into the corresponding nitriles in good yields by the treatment with sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), followed by treatment with molecular iodine in aq ammonia. The present one-pot method is very efficient and practical for the conversion of various aromatic and aliphatic esters into the corresponding nitriles.     

A Facile One-Pot Conversion of Aldehydes into Nitriles

A facile one-pot synthesis of nitriles starting with aldehydes has been developed employing hydroxylamine hydrochloride in dimethylsulfoxide at 100°C.     

A facile synthesis of new tetrahydropyrido[4,3-d]pyrimidine derivatives

The one-pot reaction of 1-benzylpiperidin-4-one with different nitriles in the presence of triflic anhydride affords substituted tetrahydropyrido[4,3-d]pyrimidines. Reaction with methylthiocyanate forms the corresponding methylthio substituted tetrahydropyridopyrimidines which can be easily converted into dimethoxy and dicarbonyl derivatives.