Alpha-Oxygenation by Acylation-Rearrangement of Nitrones

The acylation-rearrangement of N-alkylnitrones with acid chlorides and triethylamine affords a new method for the (alpha)-oxygenation of aldehydes and cyclic ketones via (alpha)-acyloxy imines. The reaction apparently proceeds by initial acylation of the nitrone oxygen, proton removal, and {3,3}-sigmatropic rearrangement of the resulting N-vinyl-O-acylhydroxylamine. Oxygen-18 labeling studies in one case showed that no scrambling of the carbonyl oxygens occurs during the rearrangement. Hydrolysis of the product imines provides the (alpha)-acyloxy aldehydes and cyclic ketones. The overall yields for the two- or three step reaction sequence are good, the conditions are quite mild, and the use of electrophilic oxidizing agents is obviated.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2014

Author dc:creator

• Cummins, Clark Hughes

• Chemistry, Organic

Identifier

(UMI)AAI8409762

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/70232