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Title:Development of a Lewis Base Catalyzed Selenocyclization Reaction
Author(s):Collins, William
Doctoral Committee Chair(s):Denmark, Scott E.
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Organic
Abstract: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.
Issue Date:2009
Type:Text
Language:English
Description:345 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2009.
URI:http://hdl.handle.net/2142/84341
Other Identifier(s):(MiAaPQ)AAI3391917
Date Available in IDEALS:2015-09-25
Date Deposited:2009


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