University of Illinois at Urbana-Champaign
Development of a Lewis Base Catalyzed Selenocyclization Reaction
Abstract
dc:description"A variety of chiral, ""soft"" Lewis base donors were prepared and tested in the selenofunctionalization reaction. An enantioselective process was never realized. Mechanistic investigations have revealed that the seleniranium ion intermediate (which is formed after delivery of the electrophilic selenium source to the olefin, and is the stereodetermining event in this transformation) is configurationally unstable under the reaction conditions. In particular, rapid deselenylation and subsequent racemization of the seleniranium ion has been shown to occur in the presence of alcohol and olefin nucleophiles. Investigations into retarding the rate of racemization of the seleniranium ion intermediate have revealed that electron-poor and sterically encumbered arylselenides are less prone to racemize in the presence of nucleophiles."
Degree
thesis:*- 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
- 2015
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- Collins, William
- Contributors dc:contributor
-
- Denmark, Scott E.
Subjects
dc:subject × 1Rights
- Language dc:language
- eng
Identifiers
dc:identifier.*- Identifier
- (MiAaPQ)AAI3391917
- OAI identifier oai:identifier
- oai:www.ideals.illinois.edu:2142/84341