Reaction of N-alkoxycarbonylaziridines with nitriles

The acid catalysed reaction of acetonitrile or benzonitrile with N-alkoxycarbonylaziridines, 1a and 1b yields the corresponding 1-alkoxycarbonyl-2-imidazolines, 2ax, 2ay, and 2bx. The imidazolines obtained by the reaction of N-ethoxycarbonyl-2,3-tetramethyleneaziridine (1c) with acetonitrileor benzonitrile are labile and are readily hydrolysed to trans-cyclohexane-1,2-diamine derivatives (3cx or 3cy). The nitrile-addition supposedly proceeds S_N2 type CN bond cleavage and CN bond formation.     

Reaction of metalated nitriles with enones

[reaction: see text] There have been a number of reports of the kinetic conjugate (1,4) addition of metalated arylacetonitriles to enones. Several proposals have been made to explain this behavior based on nucleophile structure or aggregation state or on the HSAB properties of the reactants. A reexamination of these studies showed that in each case the 1,4 adducts resulted from equilibration of the kinetically formed 1,2 adducts to the more stable 1,4 adducts. Thus, no conclusions about the origins of 1,4 selectivity can be drawn from these experiments. The 1,2 addition, retro-1,2 addition, 1,4 addition, and retro-1,4 addition of lithiophenylacetonitrile to benzylideneacetone were examined, and a free energy level diagram was constructed for the reaction.     

Reaction of chlorine fluosulfate with perfluorocarboxylic acid nitriles

Conclusions The reaction of chlorine fluosulfate with perfluorocarboxylic acid nitriles, using an equimolar ratio of the reactants and the corresponding order of mixing them, gives N-chloroiminoperfluoroacyl fluosulfates in high yield, while the use of excess chlorine fluosulfate gives perfluoroacyl fluosulfates and pyrosulfuryl difluoride.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2370–2373, October, 1981.     

Reaction of triethyl phosphite withβ-substituted nitriles

Conclusions Propionitriles having hydroxy, acetate, and phenoxy groups in the-position are capable of undergoing the Arbuzov rearrangement with triethyl phosphite to form diethyl-cyanoethylphosphonate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2089–2090, September, 1967.     

gamma-hydroxy unsaturated nitriles: chelation-controlled conjugate additions

[reaction--see text] Chelation between gamma-hydroxy unsaturated nitriles and Grignard reagents promotes an otherwise difficult anionic conjugate addition reaction. The intermediate chelate is readily generated by deprotonation with t-BuMgCl followed by the addition of a second Grignard reagent that triggers an intramolecular conjugate addition. Structurally diverse Grignard reagents add with equal efficiency, providing an intermediate anion that stereoselectively alkylates BnBr in an overall addition-alkylation reaction.     

Titanium-mediated synthesis of bicyclic cyclopropylamines from unsaturated nitriles

Here we report an easy synthesis of bicyclic primary cyclopropylamines directly from unsaturated nitriles. The described reaction involves Ti(II)-mediated intramolecular coupling of alkene and nitrile moieties.     

Reaction of diazoalkanes with unsaturated compounds

A THF solution of diazopropyne was obtained in 60% yield by the reaction of a 30% aqueous solution of methylamine withN,N′-dinitroso-N,N′-dipropargylterephthalodiamide. The reactions of diazopropyne with methyl acrylate and methyl methacrylate giving various ethynylpyrazolines as well as its CuCl-catalyzed decomposition in the presence of norbornene or norbornadiene yielding ethynylcyclopropanes were studied. The main products of catalytic deazotization of diazopropyne in the absence of unsaturated compounds are isomericE- andZ-hex-3-ene-1,5-diynes resulting from propargylene dimerization. For Part 12, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2278–2282, November, 1998.     

Reaction of unsaturated sulfoxides with alkyllithiums

Nucleophilic attack of methyllithium on allene sulfoxides offers a stereospecific access to sulfur-free allenes. Reaction of phenylsulfinyl substituted diene $\text{15}$ leads via a benzilic-type rearrangement to phenyl substituted diene $\text{18}$.     

Reaction of iodotrinitromethane with unsaturated compounds

Conclusions The reaction of iodotrinitromethane with olefins takes place by both the O- and the C-alkylation scheme, in which connection the direction of the reaction depends on the structure of the olefin and on the solvent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 621–625, March, 1968.     

Reaction of tetra-n-butylmercaptodiborane with unsaturated compounds

Summary Tetra-n-butylmercaptodiborane reacts with unsaturated compounds at 70–80° in the presence of pyridine to form esters of alkylthioboric acids.     

Reduction of unsaturated adamantyl-containing nitriles with lithium aluminum hydride in 2-methyltetrahydrofuran

Reduction of unsaturated adamantyl-containing nitriles with lithium aluminum hydride in 2-methyltetrahydrofuran was examined. It was found that under the synthesis conditions a simultaneous reduction of the double bond and the nitrile group successfully occurred. The presence of bulky substituents in the α-position to the adamantyl moiety of nitriles led to a significant increase in the synthesis duration. A satisfactory yield of the target compounds was achieved only by increasing the temperature and using a two-fold excess of lithium aluminum hydride.     

Regio- and stereodirectivity in the reactions of isoquinolinium ylides with unsaturated nitriles

Reactions of isoquinolinium ylides with arylmethylenemalonitriles involve 1,3-dipolar cycloaddition, with the highly regio- and stereoselective formation of 2-aryl-3-benzoyl(or carbamoyl)1,1-dicyano-2,3-trans-1,2,3,10b-tetrahydropyrrolo[2, 1-a]isoquinolines. In contrast, N-phenacylisoquinolinium ylide reacts with aryl-methylenecyanothioacetamides differently, proceeding regio- and stereoselectively to give 4-aryl-2-hydroxy-3-(1-isoquinolinio)-2-phenyl-3-cyano-3,4-trans-1,2,3,4-tetrahydropyridine-6-thiolates.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2593–2599, November, 1990.