Facile and Versatile Room-Temperature Synthesis of N,N-Disubstituted Cyanoacetamides from Malonic Ester Chloride

A general method for the synthesis of various N,N-disubstituted cyanoacetamides from readily available methyl malonyl chloride and secondary amines, including sterically demanding aliphatic and aromatic amines, is described.     

Activated Nitriles in Heterocyclic:Synthesis Novel Syntheses of Imidazo[2,1-b]-1,3-Thiazine Derivatives

Abstract

Several new imidazo[2,1-b]-1,3-thiazine derivatives 4a–c, 8a–c, and 11a–c were synthesised via the reaction of 5,5-diphenyl-2-thiohydantoin (1) with αβ -unsaturated nitriles 2a–c, 5a–c, and 9a–c. The structures of the products were established on the basis of elemental analyses, IR, and ¹H-NMR spectral data.     

Vanadium‐Catalyzed Solvent‐Free Synthesis of Quaternary α‐Trifluoromethyl Nitriles by Electrophilic Trifluoromethylation

The direct electrophilic trifluoromethylation of silyl ketene imines (SKIs) with hypervalent iodine reagents leads to the formation of quaternary α‐trifluoromethyl nitriles in good yields. This new reaction has been carried out with a variety of substituted SKIs under solvent‐free conditions using a vanadium(IV) catalyst (5 mol %). The corresponding products may be transformed into useful organofluorine building blocks.     

Ureidopeptide‐Based Brønsted Bases: Design,Synthesis and Application to the Catalytic Enantioselective Synthesis of β‐Amino Nitriles from (Arylsulfonyl)acetonitriles

The addition of cyanoalkyl moieties to imines is a very attractive method for the preparation of β‐amino nitriles. We present a highly efficient organocatalytic methodology for the stereoselective synthesis of β‐amino nitriles, in which the key to success is the use of ureidopeptide‐based Brønsted base catalysts in combination with (arylsulfonyl)acetonitriles as synthetic equivalents of the acetonitrile anion. The method gives access to a variety of β‐amino nitriles with good yields and excellent enantioselectivities, and broadens the stereoselective Mannich‐type methodologies available for their synthesis.     

THE USE OF MALONONITRILE IN THE SYNTHESIS OF NOVEL α-AMINO NITRILES

Continuing earlier studies designed to obtain compounds of pharmaceutical interest, we used acetyl acetone (1, R=CH₃) and ethyl acetoacetate (1, R=OEt) for the preparation of some novel α-amino nitriles (3, 6 and 7). The structures of the new ring systems have been confirmed by IR, NMR and mass spectral data.     

LiBr: A Mild Lewis Acid Catalyst for Efficient One-Pot Synthesis of α-Amino Nitriles

α-Amino nitriles are synthesized in a one-pot, three-component coupling of aldehydes, amines, and trimethylsilyl cyanide using a catalytic amount of LiBr at ambient temperature.     

Samarium Diiodide-Induced Reductive Cleavage of Se-St Bond in Arylselenotrimethylsilane Leading to the Formation of Samarium Arylselenolate: Synthesis of β-Arylseleno Estsrs and β-Arylseleno Nitriles

Theapplicationofsamariumdiiodideinorganicsynthesishasreceivedmoreandmoreattenhoninthelastdecadel4.ItisapoWerfuloneelectrontransferreductant.OurpreviousworkonthereduchvecleavageofC-S,S-S,Se-Se,Te-TeandS-StbondwithSInly-'hasledustoinvershgatethereduchvecleavageofSe-StbondbySInI2.Organoseleniumcompoundshaveattractedconsiderableinterestasreagentsandintermedieatesinorganicsynthesisrecently'-".Somemethodsforthepreparationof0selenoesterand6-selenonitrilehavebeenreported.AusefulapproachistheMi…     

1-R-3,3-dialkyl-6,7-ethylenedioxy-3,4-dihydroisoquinolines

A three component “one-pot” condensation of 1,2-ethylenedioxybenzene and RCN nitriles with isobutylene oxide, isobutyraldehyde, or cyclohexanecarboxaldehyde in the presence of conc. H₂SO₄ gives 1-R-3,3-dialkyl-6,7-ethylenedioxy-3,4-dihydroisoquinolines. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1198–1203, August, 2005.     

Novel synthesis of 2-aminopentanedinitriles from 2-(bromomethyl)aziridines and their transformation into 2-imino-5-methoxypyrrolidines and 5-methoxypyrrolidin-2-ones

1-Arylmethyl-2-(bromomethyl)aziridines were transformed into 2-[N-(arylmethyl)amino]pentanedinitriles upon treatment with an excess of potassium cyanide in DMSO through an unprecedented and peculiar reaction mechanism, involving base-induced ring opening of intermediate 2-(cyanomethyl)aziridines into allylamines, followed by migration of the double bond out of the conjugation towards aldimines via enamine intermediates. The resulting aminopentanedinitriles served as substrates for the synthesis of novel 2-imino-5-methoxypyrrolidines upon treatment with sodium methoxide in methanol, which were either acetylated at the free imino group to afford the more stable N-acetylimino derivatives or hydrolyzed towards the corresponding synthetically relevant 5-methoxypyrrolidin-2-ones.     

Synthesis of alkyl iodides/nitriles from carbonyl compounds using novel ruthenium tris(2,2,6,6-tetramethyl-3,5-heptanedionate) as catalyst

Aldehydes and ketones were hydrogenated to the corresponding alcohols, which were then transformed in situ into their respective iodides and nitriles in good yields. A structurally well-defined O-containing transition metal complex, Ru (TMHD)₃, was found to be the active catalyst for hydrogenation, iodination and cyanation reactions. It has high affinity for the transformation of benzylic alcohols to iodides and nitriles.