Nitrile allylic

A recyclable system of Pd nanoparticulates in water for hydrogenation of alkenes such as conjugated carbonyl compounds, esters, nitriles, allylic alcohols and ethers, styrenes, has been developed. ... 

Nitriles. Allylic cyanides are (Ph3P)4Pd-catalyzed transformation provides a way of controlled functioe... 

Allyl cyanide (3-butenoic acid nitrile, allyl carbylamine, vinylacetonitrile) n. CH2=CHCH2CN. Used as a crosslinking agent. 

Kiricsi et al. [243,244] investigated the interconversion of unsaturated C4 nitriles (allyl cyanide, crotononitrile, and methacrylonitrile) under basic conditions. IR-spectroscopic studies of this reaction in butyl-lithium in the liquid phase [243] revealed the existence of resonance stabilized carbanionic intermediates. The investigation of this reaction over zeolite catalysts (Na-Y and Na-Y impregnated with NaNs to obtain strong basic sites) [244] suggests the presence of a common anionic intermediate, as in the case of the liquid phase reaction. The strongly basic Na/Na-Y was able to interconvert all nitriles, while the Na-Y catalyzed only double bond migration, i.e., interconversion of allyl cyanide and crotononitrile. 

Acid chlorides and bromides, allyl halides, a-halo-ketones, esters, amides and nitriles react at 25° within 3 minutes. Vinyl and aryl halides are inert. 

Aryl and vinylic bromides and iodides react with the least substituted and most electrophilic carbon atoms of activated olefins, e.g., styrenes, allylic alcohols, a,p-unsaturated esters and nitriles. 

Allylic amine is a less reactive leaving group[7], but the allylic ammonium salts 214 (quaternary ammonium salts) can be used for allylalion(l30,131]. Allylic sulfonium salts are also used for the allylation[130]. The allylic nitrile in the cyclic aminonitrile 215 can be displaced probably via x-allylic complex formation. The possibility of the formation of the dihydropyridinium salts 216 and subsequent conjugate addition are less likelyfl 32],... 

Allylalion of the alkoxymalonitrile 231 followed by hydrolysis affords acyl cyanide, which is converted into the amide 232. Hence the reagent 231 can be used as an acyl anion equivalent[144]. Methoxy(phenylthio)acetonitrile is allylated with allylic carbonates or vinyloxiranes. After allylation. they are converted into esters or lactones. The intramolecular version using 233 has been applied to the synthesis of the macrolide 234[37]. The /i,7-unsaturated nitrile 235 is prepared by the reaction of allylic carbonate with trimethylsilyl cyanide[145]. 

The allyl cyanoacetate 731 can be converted into an a, /3-unsaturated nitrile by the decarboxylation-elimination reaction[460], but allyl malonates cannot be converted into unsaturated esters, the protonation and allylation products being formed instead. 

Metallic Pd is a good catalyst for the conversion of the primary azide 34 into the nitrile 35 in the presence of a hydrogen acceptor such as diphenylacety-lene[33]. By this method, organic halides can be converted into nitriles without increasing the carbon number. Reaction of the azidoformate 36 with an allylic... 

Nickel peroxide is a solid, insoluble oxidant prepared by reaction of nickel (II) salts with hypochlorite or ozone in aqueous alkaline solution. This reagent when used in nonpolar medium is similar to, but more reactive than, activated manganese dioxide in selectively oxidizing allylic or acetylenic alcohols. It also reacts rapidly with amines, phenols, hydrazones and sulfides so that selective oxidation of allylic alcohols in the presence of these functionalities may not be possible. In basic media the oxidizing power of nickel peroxide is increased and saturated primary alcohols can be oxidized directly to carboxylic acids. In the presence of ammonia at —20°, primary allylic alcohols give amides while at elevated temperatures nitriles are formed. At elevated temperatures efficient cleavage of a-glycols, a-ketols... 

The first, and so far only, metal-catalyzed asymmetric 1,3-dipolar cycloaddition reaction of nitrile oxides with alkenes was reported by Ukaji et al. [76, 77]. Upon treatment of allyl alcohol 45 with diethylzinc and (l ,J )-diisopropyltartrate, followed by the addition of diethylzinc and substituted hydroximoyl chlorides 46, the isoxazolidines 47 are formed with impressive enantioselectivities of up to 96% ee (Scheme 6.33) [76]. 

Zinc-tartrate complexes were applied for reactions of both nitrones and nitrile oxides with allyl alcohol and for both reaction types selectivities of more than 90% ee were obtained. Whereas the reactions of nitrones required a stoichiometric amount of the catalyst the nitrile oxide reactions could be performed in the presence of 20 mol% of the catalyst. This is the only example on a metal-catalyzed asymmetric 1,3-dipolar cycloaddition of nitrile oxides. It should however be no-... 

The reaction works well with primary alkyl halides, especially with allylic and benzylic halides, as well as other alkyl derivatives with good leaving groups. Secondary alkyl halides give poor yields. Tertiary alkyl halides react under the usual reaction conditions by elimination of HX only. Nitriles from tertiary alkyl halides can however be obtained by reaction with trimethylsilyl cyanide 4 ... 

Ammoxidation refers to a reaction in which a methyl group with allyl hydrogens is converted to a nitrile group using ammonia and oxygen in the presence of a mixed oxides-hased catalyst. A successful application of this reaction produces acrylonitrile from propylene ... 

It has been reported that an allylic C-Si bond can be cleaved by tetrabutylammonium fluoride to give an anionic allylic species, which chemoselectively adds to carbonyl compounds (nitriles, esters, and epoxides failed) to form homoallylsilyloxy compounds13. 

The titanium(IV) chloride catalyzed addition of allylic silanes to (E)-(2-nitroethenyl)benzene affords y,<5-unsaturated nitronates which, on treatment with low valent titanium species [generated in situ from titanium(IV) and zinc], give y,<5-unsaturated nitriles. For example, [(Zs)-2-butenyl]-(dimethyl)phenylsilane underwent reaction with ( )-(2-nitroethenyl)benzene to give 3-methyl-2-phenyl-4-pentenenitrile in 65 % yield as a 3 1 mixture of diastereomers of unassigned configuration22. 

Silyl enol ethers and ketene acetals derived from ketones, aldehydes, esters and lactones are converted into the corresponding o/i-unsaturated derivatives on treatment with allyl carbonates in high yields in the catalytic presence of the palladium-bis(diphenylphosphino)ethane complex (32). A phosphinc-free catalyst gives higher selectivity in certain cases, such as those involving ketene acetals. Nitrile solvents, such as acetonitrile, are essential for success. 

Vinyl sulfones such as 262 are smoothly converted to a,) -unsaturated nitriles such as 263 on treatment with KCN in the presence of dicyclohexyl-18-crown-6 in refluxing t-butyl alcohol (equation 155)148. The reaction conditions are compatible with base-labile functionalities such as a methoxycarbonyl group (equation 156)148. This method can be used in the preparation of the sesquiterpene aldehyde nuciferal from allyl phenyl sulfones. 

Allyl- -diathylester 204 Allyl-(2-methyl-allyl)- -diathylester 202 -amid-nitril (2,2-disubst.) 113 Amino- -diathylester 613 Benzyl- -diathylester 204, 208, 210 Benzyl- -dinitril 559 Benzyliden- -diathylester 208, 210 Benzyliden- -diathylester-nitril 206 Benzyliden- -dinitril 559, 643 ter.-Butyl- -nitril 114 Cyclohexyl- -athylester-nitril 206 Cyclohexyl- -diathylester 204 Cyclohexyl- -dinitril 559 Cyclohexyliden- -athylester-nitril 206 Cyclohexyliden- -dinitril 559 (1-Cyclopropyl-athyliden)- -dinitril 666 Diathyl- -amid-nitril 113 -diester 640... 

Alkenylboranes (R2C=CHBZ2 Z — various groups) couple in high yields with vinylic, alkynyl, aryl, benzylic, and allylic halides in the presence of tetra-kis(triphenylphosphine)palladium, Pd(PPh3)4, and a base to give R C CHR. 9-Alkyl-9-BBN compounds (p. 1013) also couple with vinylic and aryl halides " as well as with a-halo ketones, nitriles, and esters.Aryl halides couple with ArB(IR2 ) species with a palladium catalyst. ... 

In a, 3-unsaturated ketones, nitriles, and esters (e.g., 125), the y hydrogen assumes the acidity normally held by the position a to the carbonyl group, especially when R is not hydrogen and so cannot compete. This principle, called vinylology, operates because the resonance effect is transmitted through the double bond. However, because of the resonance, alkylation at the a position (with allylic rearrangement) competes with alkylation at the y position and usually predominates. 

There is generally little or no competition from 1,2 addition (to the C=0). However, when R is allylic,l,4 addition is observed with some substrates and 1,2 addition with others. The compound R2CuLi also add to a,P-unsaturated sulfones but not to simple aP-unsaturated nitriles. Organocopper reagents RCu (as well as certain R2CuLi) add to ocP-unsaturated and acetylenic sulfoxides. ... 

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