Cyanomethyl copper

Cyanomethyl copper has been utilised in the one-step synthesis of 7,5-unsatu-rated nitriles from allylic halides [82]. The reaction is carried out in THF-pen-tane at -25°, the reagent being prepared in situ from cyanomethyl lithium and copper (I) iodide, prior to the addition of the halide. The yields are excellent, for example, trans-homogeranyl cyanide (26) and 5-iodo-trans-dodec-4-ene nitrile (27) were each prepared in 92% yield. 

Compounds 133, prepared by the condensation of benzotriazole with aldehydes R HO (R1 = H, Pr or Ph) and 7V-octylaminoacetonitrile, react with sodium tetrafluoroborate to give the cyanomethyl derivatives 134. The latter are de-cyanomethylated by the action of copper(II) sulphate. Treatment of 133 with Grignard reagents affords the analogues 135 (R2 = Ph or PhCH2) and thence the secondary amines 136130. 

Metal-containing compounds, Zinc Compounds (Continued) (Carboethoxyalkyl)zinc iodide, 220 (Carboethoxyethyl)zinc iodide, 220 (Carboethoxypropyl)zinc iodide, 220 Chlorotrimethylsilane-Zinc, 82 (Cyanomethyl)zinc bromide, 221 Dibromomethane-Zinc-Copper(I) chloride, 93... 

Cyanomethylation. Efficient catalytic cyanomethylation reactions of carbonyl compounds with TMSCH2CN have been reported in the presence of catalytic copper complex (CuF-3PPh3-2EtOH) and a stoichiometric amount of (EtO)3SiF. The reaction is followed by a desilylation step, yielding the... 

A copper fluoride phosphine complex catalyzes the cyanomethyl addition to ketone carbonyls using trimethylsilylacetonitrile possibly through transmetalation aided by triethoxyfluorosilane (Scheme 3-136). ... 

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