Conversion to nitriles

The discovery of a Bacillus sp. strain capable of degrading aldoximes via their conversion to nitriles prompted the isolation and purification of an enzyme capable of producing the syn geometrical isomer of phenylacetaldoxime from A-hydroxy-L-phenylalanine, suggesting that amino acid-derived aldoximes are biosynthesized and metabolized in microorganisms like in plants ". 

Touaux, B., Texier-Boullet, F., and Hamelin, 1.1998. Synthesis of oximes, conversion to nitrile oxides and their subsequent 1,3-dipolar cycloaddition reactions under microwave irradiation and solvent-free reaction conditions. Heteroatom Chemistry, 9 351-54. 

A variety of thioamides possessing either mono- or di-alkyl substitution on the nitrogen can undergo the Eschenmoser coupling reaction. Primary thioamides are not acceptable substrates because of their ready conversion to nitriles under the condensation conditions. Although alkylation proceeds more readily on secondary rather than tertiary thioamides, use of the latter allows subsequent sulfur extrusion to... 

Scheme 4 Compound (45) prepared from a-santonin (41), on reduction afforded alcohol (46), which was converted to derivative (48) by standard organic reaction. Irradiation of (48) in benzene at room temperature followed by reflux in tetrahydrofuran and 2-propanol, produced 15-oxime derivative (49). Its conversion to nitrile (50) was achieved by treatmente with acetic anhydryde in pyridine. Dehydration of (50) followed by decyanation, yielded compound (52). Its acetonide derivative (53), was converted to compound (54), whose convertsion to rishitin (40), was achieved by heating with 0.5% PPA in ethanol...

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