An iron-catalysed synthesis of amides from nitriles and amines

The cheap, commercially available iron complex, Fe(NO₃)₃·9H₂O, has been used to catalyse the formation of amides by the addition of amines to nitriles.     

A novel synthesis of tocopheryl amines and amides

We report the synthesis of tocopheryl amines and amides from commercially available tocopherols. This synthesis improves the yield and diastereomeric purity of these biologically important compounds. The tocopheryl amines were prepared from the corresponding α- and δ-tocopherols using two distinct synthetic routes. The introduction of the C(6)-amino group can be achieved by aryl nitration/reduction or by Pd-catalyzed substitution of an aryl triflate, depending on the structure of the starting material. We also prepared the succinamide and maleamide derivatives of each amine. Tocopheryl amides are more potent pro-apoptotic anti-cancer agents than the corresponding α-tocopheryl esters. These compounds act selectively within the mitochondria of cancer cells.     

Ruthenium-catalyzed cycloisomerization-6pi-cyclization: a novel route to pyridines

[reaction: see text] Herein we report a method for the synthesis of substituted pyridines. The unsaturated ketones and aldehydes derived from the cycloisomerization of primary and secondary propargyl diynols in the presence of [CpRu(CH3CN)3]PF6 (1) are converted to 1-azatrienes which in turn undergo a subsequent electrocyclization-dehydration to provide pyridines with excellent regiocontrol.     

Ritter-type amidation of alkylboron derivatives with nitriles

A mild and facile synthesis of amides from alkylboron compounds and nitriles promoted by copper acetate and BF₃·OEt₂ at room temperature is disclosed.     

Palladium-catalyzed reactions of N-allylbenzotriazoles with amines and sulfonamides: A facile route to functionalized allylamines and N-allylsulfonamides

A variety of functionalized N-allylamines and N-allylsulfonamides are synthesized by Pd(II)-catalyzed intermolecular amination of the corresponding N-allylbenzotriazoles.     

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: aqueous hydration of nitriles to amides

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe(3)O(4)@SiO(2)) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions.     

A facile route to perylenequinone

Two-stage Ullmann and phenol coupling were effected in a singleoperation on methyl 5-bromo-1,2-dihydroxy-6,8-dimethoxynaphthalene-3-acetate to give dimethyl 5,8-dihydroxy-1,3,10,12-tetramethoxy-4,9-perylenequinone-6,7-diacetatewith ferric chloride as oxidant.     

Selective N-alkylation of amines using nitriles under hydrogenation conditions: facile synthesis of secondary and tertiary amines

Nitriles were found to be highly effective alkylating reagents for the selective N-alkylation of amines under catalytic hydrogenation conditions. For the aromatic primary amines, the corresponding secondary amines were selectively obtained under Pd/C-catalyzed hydrogenation conditions. Although the use of electron poor aromatic amines or bulky nitriles showed a lower reactivity toward the reductive alkylation, the addition of NH(4)OAc enhanced the reactivity to give secondary aromatic amines in good to excellent yields. Under the same reaction conditions, aromatic nitro compounds instead of the aromatic primary amines could be directly transformed into secondary amines via a domino reaction involving the one-pot hydrogenation of the nitro group and the reductive alkylation of the amines. While aliphatic amines were effectively converted to the corresponding tertiary amines under Pd/C-catalyzed conditions, Rh/C was a highly effective catalyst for the N-monoalkylation of aliphatic primary amines without over-alkylation to the tertiary amines. Furthermore, the combination of the Rh/C-catalyzed N-monoalkylation of the aliphatic primary amines and additional Pd/C-catalyzed alkylation of the resulting secondary aliphatic amines could selectively prepare aliphatic tertiary amines possessing three different alkyl groups. According to the mechanistic studies, it seems reasonable to conclude that nitriles were reduced to aldimines before the nucleophilic attack of the amine during the first step of the reaction.     

A facile and novel route to unprecedented manganese C4 cumulenic complexes

The theoretically characterized (DFT) C4 cumulenic species Mn(C5H4R)(dmpe) [=C=C=C=C(SnPh3)2] was obtained by photolysis of the C(sp2)-Sn bond in the vinylidene complex Mn(C5H4R)(dmpe)[=C=C(SnPh3)-C[triple bond]CSnPh3], which in turn was prepared by a thermal reaction from MnC5H4R(dmpe)(C7H8) and Ph3Sn-C4-SnPh3.     

Metal-free synthesis of amides by oxidative amidation of aldehydes with amines in PEG/oxidant system

A simple, inexpensive, and efficient one-pot synthesis of amide derivatives were achieved in good to excellent yields via the directly oxidative amidation of aldehydes with amines under PEG/Oxidant system.     

A facile route to polysubstitutedN-benzyl pyroglutamates

[reaction: see text] Base-induced coupling/cyclization reactions of alpha-sulfonylacetamide with various ethyl (Z)-2-bromo-2-propenoates have been carried out. The polysubstituted pyroglutamate carbon skeleton, with three contiguous asymmetric centers, was built up in one step. A ring-closure mechanism is proposed for the reactions.     

A novel, facile route to beta-fluoroamines by hydrofluorination using superacid HF-SbF(5)

A range of unsaturated amines and sulfonamides were converted to beta-fluoro nitrogen analogues after hydrofluorination in superacid HF-SbF(5), based on the formation of highly reactive electrophilic intermediates.     

Reactions of some benzofuran derivatives with amides,nitriles and hydrazines

When 6-acetoacetyl-5-methoxy- ( 1b ) and 5-acetoacetyl-6-methoxy-2,3-diphenylbenzofuran ( 2b ) were treated with cyanoacetamide, the corresponding pyridinecarbonitriles were obtained. Compounds 1b and 2b reacted with ethyl cyanoacetate in the presence of ammonium acetate to give the benzofuranyl-pyrone derivatives. This reaction, when carried out in presence of diethylamine, led to the formation of furochromones. Hydrazine hydrate, phenylhydrazine and semicarbazide hydrochloride reacted with 1b and 2b with the formation of the corresponding pyrazoles. The corresponding isoxazole derivatives were formed by the reaction of 1b and 2b with hydroxylamine hydrochloride.     

A facile one-carbon homologation of aryl aldehydes to amides

The easily accessible 2-aryl-1,1-dibromo-1-alkenes can be converted to amides under unusually mild conditions in good to excellent yields. Both electron-donating and electron-withdrawing substitutions on the aromatic rings are tolerated, and the reaction works well with hindered alkylamines. This simple homologation could find broad applications. [reaction: see text]     

Ruthenium-catalyzed annulation of alkynes with amides via formyl translocation

The first example of Ru-catalyzed intramolecular annulation of alkynes with amides via formyl translocation has been developed, which provides an efficient approach for the synthesis of 1H-indole-3-carbaldehydes.     

Ruthenium-catalyzed direct amination of alcohols with tertiary amines

A highly selective phosphine-based ruthenium catalyst system efficiently catalyzes the direct amination of alcohols with aliphatic tertiary amines, yielding unsymmetric tertiary amines in yields up to 87%. Ligand and solvent both affect the reaction yields significantly. The reaction can be performed with a wide variety of functionalities.     

Addition of amines to nitriles catalyzed by ytterbium amides: an efficient one-step synthesis of monosubstituted N-arylamidines

A one-step synthesis of monosubstituted N-arylamidinates via addition of amines to nitriles catalyzed by ytterbium amides is reported. The reactions with various substrates give the products in good to excellent yields with 5 mol % ytterbium at 100 degrees C under solvent-free conditions.     

A facile route to 4,5,6,7-tetrahydrothiophenes and benzothiophenes

2-Substituted tetrahydro- and cyclopentathiophenes 2 were produced in high yields by treatment of the semi-cyclic trisubstituted 1,4-diketones 1 such as 2-phenacylcyclohexan-1-one, 2-acetonylcyclohexan-1-one, and 2-phenacylcyclopentan-1-one, with Lawesson's reagent.