A new synthesis of (chiral) nitroxides involving a single electron transfer between lithium amides and molecular oxygen.
✍ Scribed by M.B. Eleveld; H. Hogeveen
- Publisher
- Elsevier Science
- Year
- 1984
- Tongue
- French
- Weight
- 209 KB
- Volume
- 25
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
Some (chiral) nitroxides have been synthesized by treatment of the corresponding lithium amides with molecular oxygen, which acts both as electron acceptor as well as oxygen atom donor. Important methods of nitroxide formation start from the corresponding amines.' Examples are treatment of an amine with e.g. AIBN or di-t-butylperoxide in the presence of molecular oxygen (with intermediate formation of aminyl radicals)2'3 or with hydrogen peroxides in the presence of tungstate, vanadate or molybdate (with intermediate formation of hydroxylamines).' In the course of our work on chiral synthesis of ketones and esters by deprotonation/ protonation using chiral lithium amides4 we have found a new nitroxide synthesis. It was discovered that treatment of secondary amines with n-butyllithium followed by addition of molecular oxygen affords the corresponding nitroxides.