University of Illinois Urbana-Champaign

On the Stereochemistry of Allylmetal-Aldehyde Condensations (Allyltrimethylsilane, Allyltributylstannane, Homoallylic Alcohols)

Weber, Eric John

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Description

Title
On the Stereochemistry of Allylmetal-Aldehyde Condensations (Allyltrimethylsilane, Allyltributylstannane, Homoallylic Alcohols)
Author(s)
Weber, Eric John
Issue Date
1985
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
Abstract
The stereochemical course of the intramolecular allylmetal-aldehyde condensation of allylsilane 3a, allylstannane 3b, and pentadienylsilane 6 has been investigated. A modest preference for the syn isomer 4 arising from a synclinal orientation of double bonds was observed with the Lewis acid catalyzed reaction of 3a. The selectivity for 4 was dependent on Lewis acid. Cyclization induced by fluoride ion resulted in a stereochemical reversal. The Lewis acid and heat induced cyclization of 3b gave a large preference for the syn isomer 4 which was interpreted in terms of an intrinsic stereoelectronic preference for a synclinal orientation of reacting double bonds in the transition state. The Lewis acid catalyzed cyclization of 6 gave a modest preference for the syn isomer 4. The syn-selectivity was independent of Lewis acid.
Graduation Semester
1985
Type of Resource
text
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http://hdl.handle.net/2142/70305

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