Studies in Asymmetric Catalysis: Lewis Base catalyzed/Lewis Acid Mediated Aldol Reactions of Ketone- and Amide Derived Nucleophiles
Heemstra, John Richard, Jr
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https://hdl.handle.net/2142/84258
Description
Title
Studies in Asymmetric Catalysis: Lewis Base catalyzed/Lewis Acid Mediated Aldol Reactions of Ketone- and Amide Derived Nucleophiles
Author(s)
Heemstra, John Richard, Jr
Issue Date
2007
Doctoral Committee Chair(s)
Denmark, Scott E.
Department of Study
Chemistry
Discipline
Chemistry
Degree Granting Institution
University of Illinois at Urbana-Champaign
Degree Name
Ph.D.
Degree Level
Dissertation
Keyword(s)
Chemistry, Organic
Language
eng
Abstract
Additionally, the use of the silicon tetrachloride---chiral phosphoramide system has proven a competent catalyst for highly selective vinylogous aldol reactions between dienolates derived from a variety of alpha,beta-unsaturated carbonyl compounds to aldehydes. These reactions provided high levels of gamma-site selectivity for a variety of substitution patterns on the dienyl unit. Both ketone- and morpholine amide-derived dienol ethers afforded excellent enantio- and diastereoselectivity in the addition to conjugated aldehydes. Although ketone-derived dienolate did not react with aliphatic aldehydes, amide-derived dienolates were found to undergo addition at reasonable rates affording high yields of vinylogous aldol product. The enantioselectivity achieved with the morpholine derived-dienolate in the addition to aliphatic aldehydes was the highest afforded to date with the silicon tetrachloride---chiral phosphoramide system. Furthermore, the ability to cleanly convert the morpholine amide to a methyl ketone was demonstrated.
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