Cyano esters, alkylation

Dehydiation with POCl, followed by N-alkylation with isobutylene, gives the cyano ester intermediate, which on treatment with methylamine yields (64), a compound having good herbicidal activity (eq. 15). 

Alkylation of p-dicarbonyl compounds, cyano esters and malonodinitrile (Table 6.9)... 

The carbonylation of functionalized alkenes in the presence of alkyl bromides and iodides under radical producing conditions gives good yields of /J-functionalized ketones (equation 95)369,370. These compounds may be formed with cyano, ester and aldehyde groups attached directly to the alkene. 

Cyano compounds liquid crystals, 12, 278 in silver(III) complexes, 2, 241 Cyanocuprates, with copper, 2, 186 Cyano derivatives, a-arylation, 1, 361 Cyanosilanes, applications, 9, 322 Cyclic acetals, and Grignard reagent reactivity, 9, 53 Cyclic alkenes, asymmetric hydrosilylation, 10, 830 Cyclic alkynes, strained, with platinum, 8, 644 Cyclic allyl boronates, preparation, 9, 196 Cyclic allylic esters, alkylation, 11, 91 Cyclic amides, ring-opening polymerization, via lanthanide catalysis, 4, 145... 

The relatively mild synthetic conditions during iterative growth of poly(benzyl ether) dendrons are tolerated by many peripheral groups (e.g. cyano, bromide functionality, alkyl ester, alkyl ether, perfluoroalkyl ether, oligo(ethylene glycol)... 

The effects of different solvents and palladium catalyst ligands on the allylic alkylation of aryl a-cyano esters have been investigated 133 up to 55% ee has been obtained in the presence of (-)-sparteine in THF at room temperature. 

This process was shown to be general, and a large family of substituted poly-p-xylylenes prepared in which X equals hydrogen, halogen, alkyl, cyano, ester, acyl, and other groupings. Advantages of this process (6, 7, 8, 9,10,11, 13) over previous routes (4) to poly-p-xylylene include... 

Substituted malonic acids are obtained by alkaline hydrolysis of alkyl-cyano esters prepared either by direct alkylation or by reduction of unsaturated cyano esters from the Knoevenagel reaction. ... 

Alkylations of boron-stabilized carbanions have been carried out with primary alkyl halides containing acetal, alkene, alkyne, chloride, cyano, ester and tosylate groups, though a ketone group was not tolerated. ... 

Cyclobutanone alkyl silyl acetals, obtained from [2-f2] cycloadditions, can be deprotected with 1 equiv of TBAF in THF to give the open-chain cyano esters in excellent yields (eq 5). When 4-chloro-2-cyanocyclobutane alkyl silyl acetals are used as substrates for this reaction, ( 7Z) mixtures of 2-cyanocycloprop-anecarboxylates are obtained by an intramolecular cyclization (eq 6). 

This reaction was studied comprehensively by Krapcho beginning as early as 1967. It is an alkali halide promoted alkylative decarboxylation of active esters (e.g., )8-keto esters, fi-diesters, a-cyano esters) in polar or dipolar aprotic solvents (e.g., DMF, DMSO, HMPA,) and is generally known as the Krapcho decarboxylation or Krapcho condition. Occasionally, it is also referred to as the Krapcho decarbalkoxylation. In addition, the corresponding decarboxylation on methyl esters is known as the Krapcho decarbomethoxylation, and the decarboxylation of ethyl esters is referred to as the Krapcho decarbo-ethoxylation. ... 

Nitrile anions are generated by treatment of an alkyl nitrile with a suitable base. These carbanionic reagent can undergo Michael addition with an appropriate conjugated ester to give aryl cyano-esters. Subsequent reduction of the cyano group... 

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