An experimental evaluation of the geometry of transition structures for oxygen transfer reactions: Use of the endocyclic restriction test

Oxygen transfer reactions giving rise to epoxides from olefins have been the topic of numerous studies with both synthetic and mechanistic emphases. In spite of considerable effort, the issue of the transition structure geometry has been a fundamental unanswered question. Our research has focused on investigating the geometry of the oxygen transfer reaction between peroxy acids and olefins, and between N-sulfonyloxaziridines and olefins. We have made use of the endocyclic restriction test to probe these transition structure geometries. This approach involves constructing systems in which the functional group that provides the oxygen moiety is joined to an olefin through tethers of varying lengths. The endocyclic restriction test, in combination with double labelling techniques, distinguishes intermolecular from intramolecular reactivity and allows limits to be placed on the trajectory of the oxygen transfer.

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

2011

Author dc:creator

• Woods, Keith Warren

Contributors dc:contributor

• Beak, Peter

• Chemistry, Organic

Statement dc:rights

• Copyright 1991 Woods, Keith Warren

Language dc:language

eng

Identifier

AAI9211040
(UMI)AAI9211040

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/20853