Aminoalcohols oxidative cleavage

Aminoalcohol Ring Cleavage of Nitrile Oxide Cycloadducts Synthesis of... 

Aminoalcohol Ring Cleavage of Nitrile Oxide Cycloadducts Synthesis of Amino Polyols, Amino Sugars, and Amino Acids... 

The oxidative cleavage of the carbon-hydroxymethyl groups could be removed from -aminoalcohols by treatment with lead tetraacetate in benzene then reduction with NaBH4 (Scheme 13.53) [73 a]. 

These results support our hypothesis that there is a retroaldol like cleavage of 3-hydroxynitrosamines which occurs in biological systems. Our results agree with the data of Kruger, Preussmann, and Blattmann. The fact that the tertiary nitros-aminoalcohols undergo the cleavage as well as their secondary counterparts demonstrates that oxidation to a ketone is not a... 

Linalool 54 was similarly synthesized through a [2,3]-Meisenheimer rearrangement by taking advantage of the facile cleavage of N—O bonds in the O-allylhydroxylamine rearrangement products (Scheme 15.111. Aminoalcohol 51 was converted to amine iV-oxide 52, which was transformed to O-allylhydroxylamine 53 under thermal conditions. This intermediate was subjected to reductive conditions, which selectively cleaved the N—O bond to unveil linalool 54. 

---