Nitriles from oxime tosylates

Hydrolysis of 2-unsubstituted 1-azirines is a potentially valuable method for the preparation of aminoaldehydes. The application of the Neber reaction to oxime tosylates derived from aldehydes does not give the aminoaldehydes.59 Instead, nitriles are produced by elimination. 

New azacyclic diterpenoid compounds were also prepared in good yields by ring expansion and only one isomer of the lactam 363 product was obtained (equation 142). However, when the oxime was tosylated, a nitrile compound resulting from ring opening was obtained in good yield (72%) as a result of the Beckmann degradation reaction. 

Damrauer and co-workers have shown that the nine-membered carbodiimide (77) can be formed in good yield by the treatment of the tosylate (329) with a strong base (Equation (36)) <80JOC1315> (see also <83JOCi694 . The mesylate derived from cyclooctanone oxime gives the nine-membered imino nitrile in 48% yield when treated with TMS-CN and Et2AICI <83JA283l>. 

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