Aldoximes from nitro compounds

In the presence of Triethylamine, PI3 or P2l4 effects the conversion of aldehyde oximes or primary nitro compounds to nitriles. For example, treatment of the aldoxime derived from phenylac-etaldehyde with 1 equiv of PI3 (CH2Cl2-Et3N, 25 °C, 15 min) affords benzyl cyanide in 83% yield (eq 10). Similarly, treatment of 1-nitrodecane with 2 equiv of PI3 (CH2Cl2-Et3N, 25 °C, 15 min) affords 1-cyanononane (82%) (eq 11). Other reagents for the direct conversion of primary nitro compounds to nitriles include Sn(SPh)4/Ph3P/DEAD, TMSI, Sulfur Dioxide and Phosphorus(III) Chloride. ... 

Many of the enzyme systems of the biosynthetic process have now been studied. A microsomal fraction from etiolated sorghum seedlings converted L-tyrosine (2) into p-hy-droxymandelonitrile (3) (Halkier and Mpller, 1991 Mpller and Poulton, 1993). The particles required only NADPH in addition to the substrate.. /V-Hydroxytyrosine (4) was shown to be an intermediate in the synthesis of the aldoxime, and an N-hydroxylating cytochrome P-450 was identified (Dewick, 1984 Halkier and M0ller, 1989,1991 Halkier et al, 1991). The A -hydroxytyrosine (4) is converted to 2-nitro-3-(p-hy-droxyphenyl)propionic acid (5), which is, in turn, converted to l-ad-nitro-2-(p-hydroxyphenyl)ethane (6). The last compound appears to be the immediate precursor to ( )-p-hy-... 

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